Phosphine-Containing Hydrogel Contact Lenses

ABSTRACT

Hydrogel contact lenses that are derived from a polymerizable composition including at least one hydrophilic monomer and at least one phosphine-containing component are described. The hydrogel of the contact lenses can be a silicone hydrogel or a non-silicone hydrogel. Use of polymerizable compositions comprising a phosphine-containing component can be cured under both inert and air atmospheres, and can be used to form hydrogel contact lenses having improved shape retention properties, having improved resistance to discoloration. Batches of hydrogel contact lenses and methods of making hydrogel contact lenses are also described.

This application claims the benefit under 35 U.S.C. §119(e) of priorU.S. Provisional Patent Application No. 61/447,152, filed Feb. 28, 2011,which is incorporated in its entirety by reference herein.

FIELD

The present disclosure is directed to silicone hydrogel contact lensesand related compositions and methods.

BACKGROUND

Commercially and clinically, hydrogel contact lenses, including siliconehydrogel contact lenses, currently dominate the contact lens market. Thematuration of the hydrogel lens market increases the pressure on lensmanufacturers to increase quality while reducing cost.

Some documents describing silicone hydrogel contact lenses include: U.S.Pat. No. 4,711,943, U.S. Pat. No. 5,712,327, U.S. Pat. No. 5,760,100,U.S. Pat. No. 7,825,170, U.S. Pat. No. 6,867,245, US20060063852,US20070296914, U.S. Pat. No. 7,572,841, US20090299022, US20090234089,and US20100249356, each of which is incorporated in its entirety byreference herein.

In free radical polymerization of polymerizable compositions, reactioninhibition can occur as a result of the presence of oxygen, either inthe form of dissolved oxygen gas present in the polymerizablecomposition, or in the form of oxygen gas present in the vapor spacesurrounding the mold before or during the curing process. Nitrogenpurging and/or the use of vacuum conditions for removing unwanted oxygenfrom the polymerizable composition, from the mold cavity, and/or fromthe curing oven can be used to keep oxygen levels low before and duringthe curing process. However, the use of nitrogen purging and vacuumconditions can add significantly increase the cost of the manufacturingprocess, of the manufacturing equipment, and thus of the final lensproduct.

Additionally, regardless of the type of atmosphere present duringfilling and curing, many polymerizable compositions do not result inhydrogel contact lens that are ophthalmically acceptable as the lensesformed from these polymerizable compositions do not adequately retaintheir molded shape after hydration or after autoclaving. In other words,many polymerizable compositions produce contact lenses havingundesirable characteristics such as being discolored, misshaped ordistorted, or not retaining their molded shapes, etc., even when thepolymerizable compositions are prepared and cured under low oxygenconditions or an inert atmosphere. Thus, there continues to be a needfor new hydrogel contact lens formulations and manufacturing methods,particularly lens formulations that do not require expensive inertatmospheres to be provided during curing, or that use inexpensiveingredients to improve lens shelf life, reduce lens distortion, orimprove lens shape retention.

SUMMARY

The present disclosure is directed to polymerizable compositions, tohydrogel contact lenses that are formed by reacting the polymerizablecompositions to form polymeric lens bodies, to batches of the hydrogelcontact lenses, to packages of the hydrogel contact lenses, and tomethods of manufacturing hydrogel contact lenses from the polymerizablecompositions.

The polymerizable compositions of the present disclosure comprise (a) atleast one hydrophilic monomer, and (b) at least one phosphine-containingcompound, wherein the phosphine-containing compound is present in anunoxidized form at the time it is combined with the at least onehydrophilic monomer in the polymerizable composition. Thephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer of the polymerizablecomposition can be a compound of structure (1):

where X₁, X₂, and X₃ are the same or different and are an alkyl group oran aryl group, or a polymerizable group. As used herein, an aryl groupis understood to refer to a functional group of substituent derived froman aromatic ring. In one example, the phosphine-containing compound canbe a polymerizable phosphine-containing compound. The structure ofstructure (1) can comprise one polymerizable group, or can comprise morethan one polymerizable group. The one or more polymerizable group ofstructure (1) can comprise an acrylate group such as, for example, amethacrylate group. The one or more polymerizable group of structure (1)can comprise a non-acrylate vinyl-containing functional group, i.e., afunctional group having a carbon-carbon double bond which is not part ofan acrylate functional group. The phosphine-containing compound cancomprise a tertiary phosphine-containing compound, i.e., a compoundhaving a tertiary phosphine group as part of its molecular structure. Asused herein, a tertiary phosphine is understood to refer to anorganophosphorous compound wherein the phosphorus atom is bonded tothree alkyl groups or three aryl groups or polymerizable groups or anycombination of three groups selected from alkyl groups, aryl groups andpolymerizable groups. The phosphine-containing compound can comprisestriphenylphosphine. The phosphine-containing compound can comprisediphenyl (4-vinylphenyl)phosphine. phosphine-containing compoundcomprises both triphenylphosphine and diphenyl (4-vinylphenyl)phosphine.The phosphine compound can be present in the polymerizable compositionin an amount from 0.01 to 5 unit parts by weight.

The polymerizable composition can contain an amount of thephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer that is effective to scavengeat least a portion of oxygen present in the polymerizable compositionduring manufacturing of a contact lens.

The polymerizable composition can contain an amount of thephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer that is effective to producea polymeric lens body having a reduced amount of axial edge lift (AEL)as compared to a second hydrogel contact lens body formed from a secondpolymerizable composition substantially identical to the polymerizablecomposition except without the phosphine-containing compound and using amanufacturing process substantially identical to the manufacturingprocess of the hydrogel contact lens.

The polymerizable composition can contain an amount of thephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer that is effective to reducedistortion of the hydrogel contact lens as compared to a second hydrogelcontact lens body formed from a second polymerizable compositionsubstantially identical to the polymerizable composition except withoutthe phosphine-containing compound and using a manufacturing processsubstantially identical to the manufacturing process of the hydrogelcontact lens.

The polymerizable composition can contain an amount of thephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer that is effective to reducediscoloration of the contact lens for at least 1 year when stored atroom temperature, as compared to a second contact lens formed from asecond polymerizable composition substantially identical to the firstpolymerizable composition except without the phosphine-containingcompound and using a manufacturing process substantially identical tothe manufacturing process of the hydrogel contact lens.

The polymerizable composition can optionally comprise at least onesiloxane monomer. The polymerizable composition can optionally compriseat least one cross-linking agent. The polymerizable composition canfurther comprise at least one hydrophobic monomer. Optionally, theingredients of the polymerizable composition can further include atleast one initiator, or at least one organic diluent, or at least onesurfactant, or at least one tinting agent, or at least one UV absorber,or at least one chain transfer agent, or combinations thereof.

As previously stated, the polymerizable composition is reacted to form apolymeric lens body which is further processed to prepare a hydrogelcontact lens. A batch of hydrogel contact lenses can be prepared bypreparing a plurality of hydrogel contact lenses. The batch of contactlenses can have lens properties making them acceptable for use ascontact lenses. For example, the contact lenses can have adequate levelsof shape retention. In one example, the level of shape retention of thehydrogel contact lens can be determined by measuring the axial edge lift(AEL) exhibited by an individual lens, or by measuring the average axialedge lift (AEL) variance for a batch of lenses. In a particular example,a batch of lenses can have an average axial edge lift (AEL) variance ofless than plus or minus 50% over a time period from two weeks to sevenyears when stored at room temperature, or, when stored under acceleratedshelf life conditions for a time period and temperature equivalent tostorage from two weeks to seven years at room temperature, as determinedbased on at least 20 individual lenses of the batch, the AEP variancepercentage determined for each of the individual lenses by the followingequation (A):

((AEL_(Final)−AEL_(Initial))/AEL_(Initial))×100  (A).

The present disclosure is also directed to hydrogel contact lenspackages. The hydrogel contact lens package can comprise a polymericlens body that is the reaction product of a polymerizable composition,the polymerizable composition comprising (a) at least one hydrophilicmonomer, and (b) at least one phosphine containing compound, wherein thephosphine-containing compound is present in an unoxidized form at thetime it is combined with the at least one hydrophilic monomer in thepolymerizable composition; a packaging solution comprising a lenshydrating agent; and a contact lens package base member having a cavityconfigured to hold the contact lens body and the packaging solution, anda seal attached to the base member configured to maintain the contactlens and the packaging solution in a sterile condition for a duration oftime equivalent to a room temperature shelf life of the contact lens.

The present disclosure is also directed to a method of manufacturing ahydrogel contact lens. The method can comprise providing a polymerizablecomposition comprising (a) at least one hydrophilic monomer, and (b) atleast one phosphine-containing compound, wherein thephosphine-containing compound is present in an unoxidized form at thetime it is combined with the at least one hydrophilic monomer in thepolymerizable composition; and reacting the polymerizable composition toform a polymeric lens body. In one example, the reacting of thepolymerizable composition is conducted in an atmosphere comprising air.In another example, the reacting of the polymerizable composition isconducted in an atmosphere consisting essentially of air. In anotherexample, the reacting of the polymerizable composition is conducted inan atmosphere comprising an inert gas at a concentration greater than isfound in air. In another example, the reacting comprises cast moldingthe polymerizable composition in a contact lens mold assembly to form apolymeric lens body.

The present method can further comprise contacting the polymeric lensbody with a washing liquid to remove extractable material from thepolymeric lens body. In some examples, the contacting removes a portionof the at least one phosphine compound from the polymeric lens body.

The present method can further comprise oxidizing at least a portion ofthe phosphine-containing compound present in the polymeric lens body, orin the hydrogel contact lens. The oxidizing can occur after thephosphine-containing compound has been combined with the hydrophilicmonomer in the polymerizable composition. The oxidizing can occur beforethe polymerizable composition is filled into a contact lens moldsection. The oxidizing can occur after the polymerizable composition hasbeen filled into a contact lens mold section. The oxidizing can occurbefore the polymerizable composition is cured to form a polymeric lensbody. The oxidizing can occur during the curing of the polymerizablecomposition to form a polymeric lens body.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are intended to provide a further explanation of the presentinvention, as claimed.

The accompanying figures, which are incorporated in and constitute apart of this application, are exemplary illustrations of the presentinvention and, together with the description, serve to explain theprinciples of the present invention.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a series of illustrations of hydrogel contact lenses.

FIG. 2 is a series of drawings illustrating measurement of axial edgelift (AEL) for different hydrogel contact lenses.

FIG. 3 is a series of photographs showing hydrogel contact lenses havingacceptable shape retention and having unacceptable levels of shapedistortion.

DETAILED DESCRIPTION

As described herein, it has now been discovered that hydrogel contactlenses can be formed from polymerizable compositions comprising (a) atleast one hydrophilic monomer, and (b) at least one phosphine-containingcompound, wherein the phosphine-containing compound is present in anunoxidized form at the time it is combined with the at least onehydrophilic monomer in the polymerizable composition.

The present hydrogel contact lenses comprise, or consist of, hydratedlens bodies comprising a polymeric component and a liquid component. Thepolymeric component comprises units of the at least one hydrophilicmonomer. The hydrophilic monomer is understood to be a non-siliconepolymerizable ingredient having only one polymerizable functional grouppresent in its molecular structure. It can therefore be understood thatthe polymeric component is the reaction product of a polymerizablecomposition comprising one or more hydrophilic monomers, and canoptionally include units of any additional polymerizable ingredientspresent in the polymerizable composition. The ingredients of thepolymerizable composition can optionally further comprise additionalmonomers or macromers or pre-polymers or polymers, or combinationsthereof. The additional monomers or macromers or pre-polymers orpolymers, or combinations thereof, can be silicon-containing compoundsor can be non-silicon compounds. As used herein, a non-silicon compoundis understood to be a compound which does not have a silicon atom in itsmolecular structure. The phosphine-containing compound which is presentin an unoxidized form when combined with the hydrophilic monomer, aswell as optional additional ingredients of the polymerizablecomposition, can be polymerizable ingredients or non-polymerizableingredients. As used herein, a polymerizable ingredient is understood tobe a compound which has a polymerizable double bond as part of itsmolecular structure. Thus, a non-polymerizable ingredient does not havea polymerizable double bond as part of its molecular structure. Whenpresent in the polymerizable composition, the at least one cross-linkingagent, the at least one hydrophilic monomer, and the at least onehydrophobic monomer of the polymerizable composition are understood tobe silicon-free polymerizable ingredients. As used herein, the at leastone cross-linking agent can be understood to comprise a singlecross-linking agent, or to comprise a cross-linking agent componentcomposed of two or more cross-linking agents. Similarly, the optional atleast one hydrophilic monomer can be understood to comprise a singlehydrophilic monomer, or to comprise a hydrophilic monomer componentcomposed of two or more hydrophilic monomers. The optional at least onehydrophobic monomer can be understood to comprise a single hydrophobicmonomer, or to comprise a hydrophobic monomer component composed of twoor more hydrophobic monomers. The optional at least one siloxane monomercan be understood to comprise a single siloxane monomer, or to comprisea siloxane monomer component composed of two or more siloxane monomers.Additionally, the polymerizable composition can optionally include atleast one initiator, or at least one organic diluent, or at least onesurfactant, or at least one oxygen scavenger, or at least one tintingagent, or at least one UV absorber, or at least one chain transferagent, or any combination thereof. The optional at least one initiator,at least one organic diluent, at least one surfactant, at least oneoxygen scavenger, at least one tinting agent, at least one UV absorber,or at least one chain transfer agent are understood to be non-siliconingredients, and can be either non-polymerizable ingredients orpolymerizable ingredients (i.e., ingredients having a polymerizablefunctional group as part of their molecular structure).

The combination of the polymeric component and the liquid component arepresent as a hydrated lens body, which is suitable for placement on aneye of a person. The hydrated lens body has a generally convex anteriorsurface and a generally concave posterior surface, and has anequilibrium water content (EWC) greater than 10% weight by weight(wt/wt). Thus, the present contact lenses can be understood to be softcontact lenses, which as used herein, refers to contact lenses that,when fully hydrated, can be folded upon themselves without breaking.

As understood in the industry, a daily disposable contact lens is anunworn contact lens that is removed from its sealed, sterilized package(primary package) produced by a contact lens manufacturer, placed on aperson's eye, and is removed and discarded after the person is donewearing the lens at the end of the day. Typically, the duration of lenswear for daily disposable contact lenses is from eight to fourteenhours, and they are then disposed of after wear. Daily disposable lensesare not cleaned or exposed to cleaning solutions prior to placement inthe eye since they are sterile prior to opening the package. A dailydisposable silicone hydrogel contact lens is a disposable siliconehydrogel contact lens that is replaced daily. In contrast, non-dailydisposable contact lenses are disposable contact lenses that arereplaced less frequently than daily (e.g., weekly, bi-weekly, ormonthly). Non-daily disposable contact lenses are either removed fromthe eye and cleaned with a cleaning solution on a regular basis, or areworn continuously without removal from the eye. The present contactlenses can be either daily disposable contact lenses or non-dailydisposable contact lenses. The present disclosure relates topolymerizable compositions comprising at least one phosphine-containingcompound which is present in an unoxidized form when combined with thehydrophilic monomer in the polymerizable composition, polymeric lensbodies that are the reaction products of these polymerizablecompositions, hydrogel contact lenses comprising these polymeric lensbodies in hydrated form, packages comprising these hydrogel contactlenses and a packaging solution in a sealed package, and methods ofmanufacturing these hydrogel contact lenses.

In one example, the present disclosure is directed to a polymerizablecomposition comprising at least one hydrophilic monomer and at least onephosphine-containing compound, wherein the phosphine-containing compoundis present in an unoxidized form at the time it is combined with the atleast one hydrophilic monomer in the polymerizable composition.

As previously stated, the phosphine-containing compound is present in anunoxidized form at the time it is combined with the at least onehydrophilic monomer in the polymerizable composition. In other words,the phosphine-containing compound is not a phosphine oxide-containingcompound, as it does not have an oxygen atom bound to the phosphorousatom of the phosphine group at the time it is added to the polymerizablecomposition. However, during the manufacturing process, thephosphine-containing compound may be oxidized and become a phosphineoxide-containing compound, such as, for example, by reacting with oxygenpresent in the polymerizable composition, or by reacting with oxygenpresent in a contact lens mold during a filling process, or by reactingwith oxygen present in an atmosphere of a curing oven during a curingprocess, or by reacting with oxygen present in a washing solutionfollowing demolding and delensing, or combinations thereof. The oxygenwhich reacts with the phosphine-containing compound during themanufacturing process can be present as dissolved oxygen gas, or asoxygen gas present in a mixture of gasses such as air, or as an oxidizersuch as hydrogen peroxide, or as a reactive oxygen species such assinglet oxygen, or combinations thereof.

The phosphine-containing compound can be an organophosphorous compound.The phosphine-containing compound can be an organophosphorous compoundhaving a tertiary phosphine present in its molecular structure. i.e., anorganophosphorous compound wherein the phosphorus atom is bonded tothree alkyl groups or three aryl groups or polymerizable groups or anycombination of three groups selected from alkyl groups, aryl groups andpolymerizable groups. In one example, The phosphine-containing compoundcan have the structure represented by formula (1):

where X₁, X₂, and X₃ are the same or different and are an alkyl group oran aryl group or a polymerizable group. The alkyl group and aryl groupcan be unsubstituted or substituted. The alkyl group can be a C1 to C10alkyl, or C1 to C5 alkyl, or C1 to C3 alkyl. The alkyl group can be astraight chain or a branched chain. The aryl group can be any functionalgroup or substituent derived from a simple aromatic ring. The aryl groupcan comprise a single aromatic ring or a fused ring structure. The arylgroup can be non-heterocyclic or heterocyclic. In an example, the arylgroup can be phenyl, benzyl, tolyl, naphthalenyl, pyridyl, orquinolinyl. As shown by the structure, in this example phosphine oxidesare not encompassed by the tertiary phosphine of structure (1).

In another example, the tertiary phosphine is trimethyl phosphine,triethyl phosphine, triisopropyl phosphine, tributyl phosphine,triisobutyl phosphine, tripentyl phosphine, triisopentyl phosphine,diethyl methyl phosphine, dimethyl phenyl phosphine, dimethyl ethylphosphine, diethyl propyl phosphine, triphenyl phosphine, tritolylphosphine, tribenzyl phosphine, diethyl phenyl phosphine, and dipropylphenyl phosphine.

Triphenyl phosphine (TPP) has the following general structure of formula(2):

Methods for preparing tertiary phosphine compounds of formula (1) areknown, such as the methods illustrated in U.S. Pat. Nos. 3,079,311, and4,150,058, both of which are incorporated in their entireties herein byreference.

The phosphine-containing compound of the present disclosure which ispresent in an unoxidized form when combined with the hydrophilic monomercan, in some examples, be a polymerizable phosphine-containing compound.In other words, the structure of the phosphine-containing compound caninclude a polymerizable group, such as, for example, a vinyl group or anacrylate or methacrylate group. In one example, the phosphine-containingcompound comprises a vinyl polymerizable group which is not part of anacrylate or methacrylate polymerizable group. The polymerizablephosphine-containing compound can be a phosphine-containing compoundcomprising at least one vinylic substituted aryl group. In an example,one, two or three of the X₁, X₂, and X₃ are a vinylic-group substitutedaryl group wherein the phosphine-containing compound can comprise atleast one vinylic group substituted aryl group. In a further example,the vinylic group can be vinyl, allyl, or other ethylenicallyunsaturated carbon chain group. In one particular example, thephosphine-containing compound can be diphenyl(4-vinylphenyl)phosphine(pTPP). Diphenyl(4-vinylphenyl)phosphine can be represented by formula(3):

The styrenic structure diphenyl(4-vinylphenyl)phosphine (pTPP) undergoespolymerization with curing of the lens formulation.

In some examples, the phosphine-containing compound which is present inan unoxidized form when combined with the hydrophilic monomer can bepresent in the polymerizable composition in an amount from about 0.01 to5 unit parts, such as from 0.02 to 2 unit parts, or from 0.05 to 1 unitpart. In an example where the phosphine-containing compound is atertiary phosphine (such as TPP or pTPP), a relatively small amount ofthe tertiary phosphine, for example, can be used in the polymerizablelens formulation. The phosphine-containing compound can be used, forexample, in the polymerizable composition in amounts of from about 0.1to about 1 unit part, or from about 0.2 to about 0.8 unit part, or fromabout 0.25 to about 0.75 unit parts, or from about 0.3 to about 0.6 unitparts, or other amounts.

The use of phosphine oxide-containing compounds as polymerizationinitiators in polymerizable compositions for forming contact lenses isknown. In accordance with the present disclosure, when thephosphine-containing composition is oxidized to a phosphineoxide-containing compound during the manufacturing process, such as, forexample, by scavenging oxygen, the amount of the phosphineoxide-containing compound in the polymerizable composition at the startof the polymerization process can be below an amount of the phosphineoxide initiator required to effectively polymerize the polymerizablecomposition and form a polymeric lens body having acceptable propertiesfor use as a contact lens. In other words, were all of thephosphine-containing compound present in the polymerizable compositionto be converted to the phosphine oxide-containing compound prior toinitiation of polymerization of the polymerizable composition, and thephosphine oxide-containing compound were the only initiator present inthe polymerizable composition, the phosphine oxide-containing compoundwould not be present in a high enough level to adequately polymerize thepolymerizable composition and form a polymeric lens body havingacceptable properties, such as shape retention, modulus, dimensionalstability over time, etc.

The present disclosure is directed to a polymerizable compositioncomprising at least one hydrophilic monomer and at least onephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer, wherein the at least onephosphine-containing compound is present in the polymerizablecomposition in an amount effective to scavenge at least a portion ofoxygen present in the polymerizable composition during the manufacturingprocess. The amount of the phosphine-containing compound can beeffective to scavenge oxygen from the polymerizable composition when thepolymerizable composition is initially prepared, or can be an amounteffective to scavenge oxygen from the polymerizable composition and thehead space in the polymerizable composition vessel as the polymerizablecomposition waits to be filled into mold sections, or can be an amounteffective to scavenge oxygen from the polymerizable composition, fromthe mold section and from the atmosphere during the process of fillingand closing the mold sections, or the amount can be effective toscavenge oxygen from the polymerizable composition, the mold sectionsand the atmosphere during the curing process, or combinations thereof.In other words, the oxidation of the phosphine-containing compound to aphosphine oxide-containing compound can occur after thephosphine-containing compound has been combined with the hydrophilicmonomer in the polymerizable composition, or before the polymerizablecomposition is filled into a contact lens mold section, or after thepolymerizable composition has been filled into a contact lens moldsection, or before the polymerizable composition is cured to form apolymeric lens body, or during the curing of the polymerizablecomposition to form a polymeric lens body, or any combination thereof.

In one example, the amount of the phosphine-containing compound which ispresent in an unoxidized form when combined with the hydrophilic monomerthat is present in the polymerizable composition can be an amount whichis effective to allow the composition to be filled into molds in thepresence of an oxygen-containing atmosphere, and to produceophthalmically acceptable contact lenses when cured. The ophthalmicallyacceptable contact lenses can be contact lenses having adequateretention of their molded shape, or contact lenses having propertiessimilar to lenses made by filling the polymerizable composition under aninert atmosphere or contact lenses having both adequate shape retentionand similar lens properties to contact lenses made by a fill processunder an inert atmosphere. For example, the oxygen-containing atmospherecan be air at ambient pressure, or an atmosphere containing more thanabout 1% oxygen gas by volume, an atmosphere containing less than about20% nitrogen gas by volume. The inert atmosphere can comprise a lowoxygen atmosphere, such as an atmosphere containing less than 80%nitrogen gas by volume, or a low pressure atmosphere, such as a vacuum.The similar lenses can be lenses formed of a substantially identicalpolymerizable composition.

In another example, the amount of the phosphine-containing compoundwhich is present in an unoxidized form when combined with thehydrophilic monomer that is present in the polymerizable composition canbe an amount which is effective to allow the composition to be reactedin the presence of an oxygen-containing atmosphere, and still produceophthalmically acceptable contact lenses, such as contact lenses havingadequate retention of their molded shape, or having properties similarto lenses cured under an inert atmosphere, or having both adequate shaperetention and similar lens properties. For example, theoxygen-containing atmosphere can be air at ambient pressure, or anatmosphere containing more than about 1% oxygen gas by volume, or anatmosphere containing less than about 20% nitrogen gas by volume. Theinert atmosphere can comprise a low oxygen atmosphere, such as anatmosphere containing less than 80% nitrogen gas by volume, or a lowpressure atmosphere, such as a vacuum. The similar lenses can be lensesformed of a substantially identical polymerizable composition.

In yet another example, the amount of the phosphine-containing compoundwhich is present in an unoxidized form when combined with thehydrophilic monomer that is present in the polymerizable composition canbe an amount effective to allow the composition to be both filled intomolds and reacted in the presence of an oxygen-containing atmospherewithout need for an inert atmosphere, and still produce ophthalmicallyacceptable contact lenses, such as contact lenses having adequateretention of their molded shape, or having properties similar to lensesfilled and cured under an inert atmosphere, or having both adequateshape retention and similar lens properties. For example, theoxygen-containing atmosphere can be air at ambient pressure, or anatmosphere containing more than about 1% oxygen gas by volume, or anatmosphere containing less than about 20% nitrogen gas by volume. Theinert atmosphere can comprise a low oxygen atmosphere, such as anatmosphere containing less than 80% nitrogen gas by volume, or a lowpressure atmosphere, such as a vacuum. The similar lenses can be lensesformed of a substantially identical polymerizable composition.

The present disclosure is also directed to a polymerizable compositioncomprising at least one hydrophilic monomer and at least onephosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer, wherein the polymerizablecomposition contains an amount of the phosphine-containing compoundeffective to produce a polymeric lens body having a reduced amount ofaxial edge lift (AEL) as compared to a second hydrogel contact lens bodyformed from a second polymerizable composition substantially identicalto the polymerizable composition except without the phosphine-containingcompound and using a manufacturing process substantially identical tothe manufacturing process of the hydrogel contact lens.

FIG. 1 is a series of illustrations of hydrogel contact lenses having noaxial edge lift (lens 10A and lens 10B) and of contact lenses havingsome degree of edge lift, ranging from minimal (lens 10C) toprogressively more severe, (lens 10D, lens 10E and lens 10F,respectively). The illustrations of FIG. 1 include dashed linesillustrating the back optic zone curve of each lens. Thus, 11A is theback optic zone curve of lens 10A, 11B is the back optic zone curve oflens 10B, 11C is the back optic zone curve of lens 10C, 11D is the backoptic zone curve of lens 10D, 11E is the back optic zone curve of lens10E, and 11F is the back optic zone curve of lens 10F. The back opticzone radius (BOZR) is illustrated by radius 12, which is the radius ofthe back optic zone cure of lens 10B (and which is the same curve, andthe BOZR, for all of lenses 10A-10F).

FIG. 2 is an illustration of the hydrogel contact lenses of FIG. 1having some degree of edge lift. The vertical lines 13C, 13D, 13E and13F illustrate the axial edge lift (AEL) of respective lenses 10C, 10D,10E, and 10F as measured from the back optic zone curve 11C, 11D, 11Eand 11F. The AEL can be measured on sectioned lenses or using othermeans known in the art. Some lens designs may intentionally include asmall amount of edge lift. An acceptable level of AEL can be less thanabout 40 micrometers, or less than about 30 micrometers. Lenses havingpoor shape retention often ‘flare out’ at the edge, displaying AELvalues greater than about 50 micrometers, such as, for example, greaterthan about 75 micrometers or greater than about 100 micrometers.

In another example, the polymerizable composition contains an amount ofthe phosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer that is an amount effectiveto reduce distortion of the hydrogel contact lens. For example, theamount of phosphine-containing compound can be effective to reducedistortion of the hydrogel contact lens as compared to a second hydrogelcontact lens body formed from a second polymerizable compositionsubstantially identical to the polymerizable composition except withoutthe phosphine-containing compound, and using a manufacturing processsubstantially identical to the manufacturing process of the hydrogelcontact lens. The distortion can be shape distortion, or can be opticaldistortion.

In a specific example, contact lenses formed from a polymerizablecomposition comprising a phosphine-containing compound which is presentin an unoxidized form when combined with the hydrophilic monomer haveacceptable levels of shape retention without impairment of the finallens properties. The presence of the phosphine containing compound inthe polymerizable composition, and in the resulting polymerized lensbodies, is effective in stabilizing the shape of the hydrogel contactlenses, while still providing a hydrogel contact lens havingophthalmically acceptable physical properties, such as, for example, anequilibrium water content greater than 30%, or an oxygen permeabilitygreater than 55 barrers, or a tensile modulus from 0.2 MPa to 0.85 MPa,or combinations thereof. Such contact lenses retain their molded shapesafter being autoclaved and fully hydrated.

FIG. 3 is a series of photographs of hydrogel contact lenses formed frompolymerizable compositions having the same components, except with (3Aand 3C) and without (3B and 3D) a phosphine-containing compound. Lenses3A and 3B were manufactured using the same process, includingpolymerization in an air atmosphere. Lenses 3C and 3D were manufacturedusing the same process, including polymerization in an inert atmosphere.The lenses formed from compositions comprising the phosphine-containingcompound had acceptable shapes (3A and 3C), while the lenses formed fromcompositions without the phosphine-containing compound had distortedshapes (3B and 3D).

In accordance with the lenses and methods of manufacturing lensesdisclosed herein, the polymerizable composition can be reacted in anatmosphere comprising air. The polymerizable composition can be reactedin an atmosphere consisting essentially of air. The polymerizablecomposition can be reacted in an atmosphere comprising air. Thepolymerizable composition can also be reacted in an atmospherecomprising an inert gas at a concentration greater than is found in air.The polymerizable composition can also be reacted in an atmospherecomprising a low concentration of an inert gas, such as an atmospherecontaining less than 80% nitrogen gas by volume. Alternatively, thepolymerizable composition can be reacted under an atmosphere containinga high concentration of an inert gas, such as a nitrogen atmosphere,including an atmosphere comprising greater than 80% nitrogen gas byvolume.

Similarly, the polymerizable composition can be stored in an atmospherecomprising air. The polymerizable composition can be stored in anatmosphere consisting essentially of air. The polymerizable compositioncan be stored in an atmosphere consisting of air. The polymerizablecomposition can also be stored in an atmosphere comprising an inert gasat a concentration greater than is found in air. The polymerizablecomposition can also be stored in an atmosphere comprising a lowconcentration of an inert gas, such as an atmosphere containing lessthan 80% nitrogen gas by volume. Alternatively, the polymerizablecomposition can be stored under an atmosphere containing a highconcentration of an inert gas, such as a nitrogen atmosphere, includingan atmosphere comprising greater than 80% nitrogen gas by volume.

Additionally, in some examples, the polymerizable composition can befilled into the mold sections in an atmosphere comprising air. Thepolymerizable composition can be filled into the mold sections in anatmosphere consisting essentially of air. The polymerizable compositioncan be filled into the mold sections in an atmosphere consisting of air.The polymerizable composition can also be filled in an atmospherecomprising an inert gas at a concentration greater than is found in air.The polymerizable composition can also be filled in an atmospherecomprising a low concentration of an inert gas, such as an atmospherecontaining less than 80% nitrogen gas by volume. Alternatively, thepolymerizable composition can be filled under an atmosphere containing ahigh concentration of an inert gas, such as a nitrogen atmosphere,including an atmosphere comprising greater than 80% nitrogen gas byvolume.

In another example, the polymerizable composition can contain an amountof the phosphine-containing compound which is present in an unoxidizedform when combined with the hydrophilic monomer that is an amounteffective to reduce discoloration of the contact lens for at least 1year when stored at room temperature, or for an equivalent period oftime under accelerated testing conditions. In some formulations, it hasbeen found that the presence of low concentrations ofphosphine-containing compounds is effective to eliminate or reduceyellowing of the hydrogel contact lenses when stored for long periods oftime. The amount of phosphine-containing compound can be effective toreduce discoloration of the contact lens as compared to a secondhydrogel contact lens body formed from a second polymerizablecomposition substantially identical to the polymerizable compositionexcept without the phosphine-containing compound and using amanufacturing process substantially identical to the manufacturingprocess of the hydrogel contact lens.

The reduction in discoloration can comprise a reduction in the level ofyellowness of the lenses. The level of yellowness can be detected usinga color analyzer. For example, the color analyzer can be based on amultiple-coordinate color system such as the CIE L*a*b* system. Thethree coordinates of the CIE L*a*b* system represent the lightness ofthe color (L*=0 yields black and L*=100 indicates diffuse white;specular white may be higher), its position between red/magenta andgreen (a*, negative values indicate green while positive values indicatemagenta) and its position between yellow and blue (b*, negative valuesindicate blue and positive values indicate yellow). When using such asystem, the reduction in the level of yellowness of the lenses cancomprise a reduction in the L* value, or a reduction in a positive b*value, or an increase in a negative b* value.

As stated above, the phosphine-containing compound which is present inan unoxidized form when combined with the hydrophilic monomer is part ofor within the unitary construction of the lens body. In one example,when the phosphine-containing compound is a polymerizablephosphine-containing compound, the phosphine-containing compound ispresent as a unit of the copolymer comprising the polymerized lens body.In such an example, the phosphine-compound can be immobilizedchemically, physically, or both chemically and physically, in the lensbody.

The phosphine-containing compound which is present in an unoxidized formwhen combined with the hydrophilic monomer can be present throughout theentire polymerized lens body. Various gradients of concentrations of thephosphine-containing compound can be present throughout the lens body,such that the concentration of the phosphine-containing compound isuniform throughout the lens body or is non-uniform throughout the lensbody. The concentration of the phosphine-containing compound can besubstantially uniform throughout the lens body and this can be achievedby adding the phosphine-containing compound in the polymerizablecomposition and distributing the phosphine-containing compound uniformlythroughout the composition prior to formation of the lens, for example,prior to filling the polymerizable composition into a mold. As anoption, the phosphine-containing compound can be added to thecomposition at least in part or completely before polymerizationcommences with the reactive components forming the lens composition. Asan option, a larger concentration of the phosphine-containing compoundcan be present at a surface(s) of the lens body where oxygen exposurecan occur.

With the present invention, the phosphine-containing compound which ispresent in an unoxidized form when combined with the hydrophilic monomeris not present due to a post-treatment on the lens body already formed,such as by a surface coating. Though, as an option, a coating of aphosphine-containing compound can be present in addition to thephosphine-containing component in the polymerizable composition. Asstated, the phosphine containing compound is part of the polymerizablecomposition used to form the lens body, is part of the polymerized lensbody following polymerization and remains part of the lens body, atleast until the polymerizable composition, the lens body, or both, areexposed to conditions that oxidize the phosphine-containing compound tobecome a phosphine oxide-containing compound. Similarly, the phosphinecontaining compound remains part of the polymerized lens body at leastuntil the polymerizable lens body is contacted by a liquid, for exampleas part of a demolding process, a delensing process, a process tooxidize remaining phosphine-containing component, a washing orextraction process, contact with a packaging solution, a sterilizationprocess, etc., that comprise part of the process of transforming thepolymeric lens body into a finished hydrogel contact lens.

While it is optional to include an additional layer on the lens surfaceof the lens body that may include a phosphine-containing compound, it isto be understood that this is not necessary and, in fact, with thepresent invention, by having a phosphine-containing compoundincorporated as part of the overall lens composition and part of theoverall lens, there is no need to have a separate coating or layer ofthe phosphine-containing compound for any purpose.

As previously discussed, the phosphine-containing compound which ispresent in an unoxidized form when combined with the hydrophilic monomeris part of the polymerizable composition which is reacted to polymerizeand form the lens body. In addition to at least one phosphine-containingcomponent, the polymerizable composition comprises at least onehydrophilic monomer. The polymerizable composition can be reacted toform a polymeric lens body. The polymer of the lens body can be ahomopolymer, or a copolymer comprising units of the hydrophilic monomer,including a crosslinked copolymer or a branched chain copolymer or alinear copolymer, or an inter-penetrating polymer network of twopolymers or copolymers, each of which is crosslinked to itself, or apseudo-interpenetrating polymer network of two polymers or copolymers,only one of which is crosslinked to itself. When thephosphine-containing component comprises a polymerizablephosphine-containing component, the copolymer of the polymeric lens bodyincludes polymerized units of the phosphine-containing component inaddition to polymerized units of the hydrophilic monomer. Optionally,the polymerizable composition can further comprise at least one siloxanemonomer, at least one cross-linking agent, at least one initiator, atleast one tinting agent; at least one UV blocking agent, andcombinations and subsets thereof.

As used herein, the hydrophilic monomer of the polymerizable compositionis understood to be a non-silicon hydrophilic monomer, and thus isdifferent from a siloxane monomer. The hydrophilicity or hydrophobicityof a monomer (including silicon-containing and non-silicon monomers) canbe determined using conventional techniques, such as, for example, basedon the monomer's aqueous solubility. For purposes of the presentdisclosure, a hydrophilic monomer is a monomer that is visibly solublein an aqueous solution at room temperature (e.g. about 20-25 degreesC.). For example, a hydrophilic monomer can be understood to be anymonomer for which 50 grams or more of the monomer are visibly fullysoluble in 1 liter of water at 20 degrees C. (i.e., the monomer issoluble at a level of at least 5% wt/wt in water) as determined using astandard shake flask method as known to persons of ordinary skill in theart. A hydrophobic monomer, as used herein, is a monomer that is visiblyinsoluble in an aqueous solution at room temperature, such thatseparate, visually identifiable phases are present in the aqueoussolution, or such that the aqueous solution appears cloudy and separatesinto two distinct phases over time after sitting at room temperature.For example, a hydrophobic monomer can be understood to be any monomerfor which 50 grams of the monomer are not visibly fully soluble in 1liter of water at 20 degrees C. (i.e., the monomer is soluble at a levelof less than 5% wt/wt in water).

Examples of hydrophilic monomers which can be included in the presentpolymerizable compositions can include, for example,N,N-dimethylacrylamide (DMA), or 2-hydroxyethyl acrylate, or2-hydroxyethyl methacrylate (HEMA), or 2-hydroxypropyl methacrylate, or2-hydroxybutyl methacrylate (HOB), or 2-hydroxybutyl acrylate, or4-hydroxybutyl acrylate glycerol methacrylate, or 2-hydroxyethylmethacrylamide, or polyethyleneglycol monomethacrylate, or methacrylicacid, or acrylic acid, or any combination thereof.

In one example, the hydrophilic monomer or hydrophilic monomer componentcan comprise or consist of a vinyl-containing monomer. Examples ofhydrophilic vinyl-containing monomers which can be provided in thepolymerizable compositions include, without limitation, N-vinylformamide, or N-vinyl acetamide, or N-vinyl-N-ethyl acetamide, orN-vinyl isopropylamide, or N-vinyl-N-methyl acetamide (VMA), or N-vinylpyrrolidone (NVP), or N-vinyl caprolactam, or N-vinyl-N-ethyl formamide,or N-vinyl formamide, or N-2-hydroxyethyl vinyl carbamate, orN-carboxy-β-alanine N-vinyl ester, 1,4-butanediol vinyl ether (BVE), orethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether(DEGVE), or any combination thereof.

In another example, the hydrophilic monomer or hydrophilic monomercomponent of the polymerizable composition can comprise or consist of ahydrophilic amide monomer. The hydrophilic amide monomer can be ahydrophilic amide monomer having one N-vinyl group, such as, forexample, N-vinyl formamide, or N-vinyl acetamide, or N-vinyl-N-ethylacetamide, or N-vinyl isopropylamide, or N-vinyl-N-methyl acetamide(VMA), or N-vinyl pyrrolidone (NVP), or N-vinyl caprolactam, or anycombination thereof. In one example, the hydrophilic monomer orhydrophilic monomer component comprises N-vinyl-N-methyl acetamide(VMA). For example, the hydrophilic monomer or monomer component cancomprise or consist of VMA. In one particular example, the hydrophilicmonomer can be VMA.

In another example, the hydrophilic vinyl-containing monomer or monomercomponent can comprise or consist of a vinyl ether-containing monomer.Examples of vinyl ether-containing monomers include, without limitation,1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE),or diethylene glycol vinyl ether (DEGVE), or any combination thereof. Inone example, the hydrophilic monomer component comprises or consists ofBVE. In another example, the hydrophilic monomer component comprises orconsists of EGVE. In yet another example, the hydrophilic vinylcomponent comprises or consists of DEGVE.

In yet another example, the hydrophilic vinyl-containing monomercomponent can comprise or consist of a combination of a firsthydrophilic monomer or monomer component, and a second hydrophilicmonomer or hydrophilic monomer component. In one example, the firsthydrophilic monomer has a different polymerizable functional group thanthe second hydrophilic monomer. In another example, each monomer of thefirst hydrophilic monomer has a different polymerizable functional groupthan the second hydrophilic monomer. In another example, the firsthydrophilic monomer has a different polymerizable functional group thaneach monomer of the second hydrophilic monomer component. In yet anotherexample, each monomer of the first hydrophilic monomer component has adifferent polymerizable functional group than each monomer of the secondhydrophilic monomer component.

For example, when the first hydrophilic monomer or monomer componentcomprises or consists of one or more amide-containing monomers, thesecond hydrophilic monomer or monomer component can comprise or consistof one or more non-amide monomers (i.e., one or more monomers each ofwhich do not have an amide functional group as part of their molecularstructures). As another example, when the first hydrophilic monomer ormonomer component comprises or consists of one or more vinyl-containingmonomers, the second hydrophilic monomer or monomer component cancomprise one or more non-vinyl monomers (i.e., one or more monomers eachof which do not have a vinyl polymerizable functional group as part oftheir molecular structures). In another example, when the firsthydrophilic monomer or monomer component comprises or consists of one ormore amide monomers each having an N-vinyl group, the second hydrophilicmonomer or monomer component can comprise or consist of one or morenon-amide monomers. When the first hydrophilic monomer or monomercomponent comprise or consists of one or more non-acrylate monomers(i.e., one or more monomers each of which do not have an acrylate ormethacrylate polymerizable functional group as part of their molecularstructures), the second hydrophilic monomer or monomer component cancomprise or consist of one or more acrylate-containing monomers, or oneor more methacrylate-containing monomers, or any combination thereof.When the first hydrophilic monomer or monomer components comprises orconsists of one or more non-vinyl ether-containing monomers (i.e., oneor more monomers each of which do not have a vinyl ether polymerizablefunctional group as part of their molecular structures), the secondhydrophilic monomer or monomer component can comprise or consist of oneor more vinyl ether-containing monomers. In a particular example, thefirst hydrophilic monomer or monomer component can comprise or consistof one or more amide-containing monomers each having an N-vinyl group,and the second hydrophilic monomer or monomer component can comprise orconsist of one or more vinyl ether-containing monomers.

In one example, when the first hydrophilic monomer or monomer componentcomprises or consists of a hydrophilic amide-containing monomer havingone N-vinyl group, the second hydrophilic monomer or monomer componentcan comprise or consist of a vinyl ether-containing monomer. In aparticular example, the first hydrophilic monomer can comprise VMA, andthe second hydrophilic monomer or monomer component can comprise BVE orEGVE or DEGVE or any combination thereof. The first hydrophilic monomercan comprise VMA and the second hydrophilic monomer can comprise BVE.The first hydrophilic monomer can comprise VMA and the secondhydrophilic monomer can comprise EGVE. The first hydrophilic monomer cancomprise VMA and the second hydrophilic monomer can comprise DEGVE. Thefirst hydrophilic monomer can comprise VMA, and the second hydrophilicmonomer component can comprise EGVE and DEGVE.

Similarly, the first hydrophilic monomer can be VMA, and the secondhydrophilic monomer or monomer component can comprise BVE or EGVE orDEGVE or any combination thereof. The first hydrophilic monomer can beVMA and the second hydrophilic monomer can be BVE. The first hydrophilicmonomer can be VMA and the second hydrophilic monomer can be EGVE. Thefirst hydrophilic monomer can comprise VMA and the second hydrophilicmonomer can be DEGVE. The first hydrophilic monomer can be VMA, and thesecond hydrophilic monomer component can be a combination of EGVE andDEGVE.

In another example, the non-silicon hydrophilic vinyl-containing monomercan have any molecular weight, such as a molecular weight less than 400daltons, or less than 300 daltons, or less than 250 daltons, or lessthan 200 daltons, or less than 150 daltons, or from about 75 to about200 daltons.

When a hydrophilic monomer or a hydrophilic monomer component is presentin the polymerizable composition, the hydrophilic monomer or monomercomponent can be present in the polymerizable composition in an amountfrom 30 to 60 unit parts of the polymerizable composition. Thehydrophilic monomer or monomer component can be present in thepolymerizable composition from 40 to 55 unit parts, or from 45 to 50unit parts by weight. When the hydrophilic monomer component of thepolymerizable composition comprises a first hydrophilic monomer ormonomer component and a second hydrophilic monomer or monomer component,the second hydrophilic monomer or monomer component can be present inthe polymerizable composition in an amount from 0.1 to 20 unit parts ofthe polymerizable composition. For example, of the total amount of from30 to 60 unit parts of hydrophilic monomer or monomer component presentin the polymerizable composition, 29.9 to 40 unit parts can comprise thefirst hydrophilic monomer or monomer component, and 0.1 to 20 unit partscan comprise the second hydrophilic monomer or monomer component. Inanother example, the second hydrophilic monomer or monomer component canbe present in the polymerizable composition from 1 to 15 unit parts, orfrom 2 to 10 unit parts, or from 3 to 7 unit parts.

As used herein, a vinyl-containing monomer is a monomer having a singlepolymerizable carbon-carbon double bond (i.e., a vinyl polymerizablefunctional group) present in its molecular structure, where, under freeradical polymerization, the carbon-carbon double bond in the vinylpolymerizable functional group is less reactive than the carbon-carbondouble bond present in an acrylate or a methacrylate polymerizablefunctional group. In other words, although a carbon-carbon double bondis present in acrylate groups and methacrylate groups, as understoodherein, monomers comprising a single acrylate or methacrylatepolymerizable group are not considered to be vinyl-containing monomers.Examples of polymerizable groups having carbon-carbon double bonds whichare less reactive than the carbon-carbon double bonds of acrylate ormethacrylate polymerizable groups include vinyl amide, vinyl ether,vinyl ester, and allyl ester polymerizable groups. Thus, as used herein,examples of vinyl-containing monomers include monomers having a singlevinyl amide, a single vinyl ether, a single vinyl ester, or a singleallyl ester polymerizable group.

In any or each of the foregoing examples, as previously discussed, theamount of the hydrophilic monomer or monomer component (e.g., the one ormore hydrophilic monomers present in the polymerizable composition) canbe from 30 to 60 unit parts of the polymerizable composition. In certainexamples, the hydrophilic monomer or mixture of monomers component canconstitute from 40 to 55 unit parts of the polymerizable composition, orfrom 45 to 50 unit parts of the composition. When VMA is present in thepolymerizable composition, it can be present in an amount from 30 unitparts to 60 unit parts. In certain examples, VMA is present in thepolymerizable composition in an amount from about 40 unit parts to about55 unit parts, or from 45 to 50 unit parts. If the hydrophilic monomers,N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), or2-hydroxylbutyl methacrylate (HOB), are present in the polymerizablecomposition as an optional second hydrophilic monomer or mixture ofmonomers, they can be present in amounts from about 3 to about 10 unitparts.

As used herein, a molecular weight is understood to refer to the numberaverage molecular weight. The number average molecular weight is theordinary arithmetic mean or average of the molecular weights of theindividual molecules present in the sample of a monomer. As theindividual molecules in a sample of monomer may vary slightly from oneanother in molar mass, some level of polydispersity may be present inthe sample. As used herein, when the siloxane monomer, or any othermonomer, macromer, pre-polymer, or polymer, of the polymerizablecomposition is polydisperse, the term “molecular weight” refers to thenumber average molecular weight of the monomer or ingredient. As oneexample, a sample of the siloxane monomer can have a number averagemolecular weight of about 15,000 daltons, but if the sample ispolydisperse, the actual molecular weights of the individual monomerspresent in the sample may range from 12,000 daltons to 18,000 daltons.

The number average molecular weight can be the absolute number averagemolecular weight as determined by proton nuclear magnetic resonance(NMR) end group analysis, as understood by persons of ordinary skill inthe art. Molecular weights may also be determined using gel permeationchromatography, as understood by persons of ordinary skill in the art,or may be provided by suppliers of the chemicals.

As used herein, unit parts is understood to mean unit parts by weight.For example, to prepare a formulation described as comprising x unitparts of a phosphine-containing compound and y unit parts of ahydrophilic monomer, the composition can be prepared by combining xgrams of the phosphine-containing compound with y grams of thehydrophilic monomer to obtain a total of y+z grams of polymerizablecomposition, or by combining z ounces of the phosphine-containingcompound with y ounces of the hydrophilic monomer to obtain a total ofy+z ounces of polymerizable composition, and so on. When the compositionfurther comprises additional optional ingredients such as, for example,x unit parts of a cross-linking agent, x grams of the cross-linkingagent are combined with z grams of the phosphine-containing compound andy grams of the hydrophilic monomer to obtain a total of x+y+z grams ofpolymerizable composition, and so on. When the composition comprises anadditional optional ingredient comprising an ingredient componentcomposed of two ingredients, such as, for example, a hydrophobic monomercomponent consisting of a first hydrophobic monomer and a secondhydrophobic monomer, in addition to the z unit parts ofphosphine-containing compound, the y unit parts of hydrophilic monomerand the x unit parts of the cross-linker, w unit parts of the firsthydrophobic monomer and v unit parts of the second hydrophobic monomerare combined to obtain a total amount of v+w+x+y+z unit parts of thepolymerizable composition. It is understood that the unit parts of theat least one hydrophobic monomer present in such a polymerizable is thesum of the unit parts of the first hydrophobic monomer and the unitparts of the second hydrophobic monomer, e.g., v+w unit parts in thisexample. Typically, a formula for a polymerizable composition will becomposed of ingredients in amounts totaling from about 90 to about 110unit parts by weight. When amounts of components of the polymerizablecomposition are recited herein as being in unit parts, it is to beunderstood that the unit parts of these component are based on a formulaproviding a total weight of the composition ranging from about 90 to 110unit parts. In one example, the unit parts by weight can be based on aformula providing a total weight of the composition ranging from about95 to 105 unit parts by weight, or from about 98 to 102 unit parts byweight.

In one example, the present disclosure is directed to hydrogel contactlenses essentially free of silicon-containing ingredients, i.e., contactlenses formed of a hydrogel containing less than 0.1% (w/w) of asilicon-containing ingredient. In another example, the presentdisclosure is directed to silicone hydrogel contact lenses. As usedherein, “silicone hydrogel” or “silicone hydrogel material” refers to aparticular hydrogel that includes a silicone (SiO) component. Forexample, a silicone hydrogel is typically prepared by combining asilicon-containing material with conventional hydrophilic hydrogelprecursors. A silicone hydrogel contact lens is a contact lens,including a vision correcting contact lens, which comprises a siliconehydrogel material. A siloxane monomer is a monomer that contains atleast one siloxane [—Si—O—Si—] linkage. In a siloxane monomer, eachsilicon atom may optionally possess one or more organic radicalsubstituents (R₁, R₂) or substituted organic radical substituents thatmay be the same or different, e.g., —SiR₁R₂O—. Similarly, a non-siliconingredient is an ingredient containing less than 0.1% (w/w) silicon.

In some examples of the present invention, the polymerizable compositioncan further comprise at least one siloxane monomer. In such an example,the polymeric lens body will include polymerized units of the at leastone siloxane monomer, and the hydrogel contact lens will comprise asilicone hydrogel contact lens. As used herein, a reactive ingredientwhich can be reacted to form a unit part of a polymer is referred to asa monomer, regardless of its size. The optional at least one siloxanemonomer can comprise a single siloxane monomer, or can comprise asiloxane monomer component composed of two or more siloxane monomers.The at least one siloxane monomer can be a hydrophilic siloxane monomer,or a hydrophobic siloxane monomer, or can have both hydrophilic regionsand hydrophobic regions, depending on the amount and location of anyhydrophilic components, such as units of ethylene glycol, polyethyleneglycol and the like, present in the molecular structure of the siloxanemonomers.

For example, the siloxane monomer can contain hydrophilic componentswithin the main chain of the siloxane molecule, can contain hydrophiliccomponents within one or more side chains of the siloxane molecule, orany combination thereof. For example, the siloxane monomer can have atleast one unit of ethylene glycol adjacent to a polymerizable functionalgroup in the main chain of the siloxane molecule. As used herein,adjacent is understood to mean both immediately adjacent, and separatedonly by 10 or fewer carbon atoms. The at least one unit of ethyleneglycol adjacent to a polymerizable functional group in the main chain ofthe siloxane molecule can be separated from the polymerizable functionalgroup by a carbon chain 1-5 units in length (i.e., where the ethyleneglycol unit is bonded to the first carbon in the carbon chain 1-5 unitsin length, and the polymerizable functional group is bonded to the lastcarbon of the carbon chain 1-5 units in length, in other words, theethylene glycol unit and the polymerizable group are not immediatelyadjacent but are separated by 1-5 carbon atoms). The siloxane monomercan have at least one unit of ethylene glycol adjacent to polymerizablefunctional groups present on both ends of the main chain of the siloxanemolecule. The siloxane monomer can have at least one unit of ethyleneglycol present in at least one side chain of the siloxane molecule. Theat least one unit of ethylene glycol present in at least one side chainof the siloxane molecule can be part of a side chain bonded to a siliconatom of the main chain of the siloxane molecule. The siloxane moleculecan have both at least one unit of ethylene glycol adjacent topolymerizable functional groups present on both ends of the main chainof the siloxane molecule, and at least one unit of ethylene glycolpresent in at least one side chain of the siloxane molecule.

In one example of the present disclosure, when present in thepolymerizable composition, the optional at least one siloxane monomercan be a multifunctional siloxane monomer. If the siloxane monomer hastwo functional groups, such as two methacrylate groups, it is abifunctional monomer. If the siloxane monomer has three functionalgroups, it is a trifunctional monomer.

The optional siloxane monomer can be a siloxane monomer having apolymerizable functional group present on one end of the main chain ofthe monomer. The siloxane monomer can be a siloxane monomer having apolymerizable functional group on both ends of the main chain of themonomer. The siloxane monomer can be a siloxane monomer having apolymerizable functional group present on at least one side chain of themonomer. The siloxane monomer can be a siloxane monomer having apolymerizable functional group present on only one side chain of themonomer.

The optional siloxane monomer of the polymerizable composition can be anacrylate-containing siloxane monomer, in other words, a siloxane monomerhaving at least one acrylate polymerizable functional group as part ofits molecular structure. In one example, the acrylate-containingsiloxane monomer can be a methacrylate-containing siloxane monomer,i.e., a siloxane monomer having at least one methacrylate polymerizablefunctional group as part of its molecular structure.

The optional siloxane monomer can be a siloxane monomer having a numberaverage molecular weight of at least 3,000 daltons. In another example,the siloxane monomer can be a siloxane monomer having a molecular weightof at least 4,000 daltons, or of at least 7,000 daltons, or of at least9,000 daltons, or of at least 11,000 daltons.

The optional siloxane monomer can be a siloxane monomer having amolecular weight less than 20,000 daltons. In another example, thesiloxane monomer can be a siloxane monomer having a molecular weightless than 15,000 daltons, or less than 11,000 daltons, or less than9,000 daltons, or less than 7,000 daltons, or less than 5,000 daltons.

The optional siloxane monomer can be a siloxane monomer having amolecular weight from 3,000 daltons to 20,000 daltons. In anotherexample, the siloxane monomer can be a siloxane monomer having amolecular weight from 5,000 daltons to 20,000 daltons, or from 5,000daltons to 10,000 daltons, or from 7,000 daltons to 15,000 daltons.

In one example, the optional siloxane monomer has more than onefunctional group and has a number average molecular weight of at least3,000 daltons.

The optional siloxane monomer can include poly(organosiloxane) monomersor macromers or prepolymers, such as, for example,3-[tris(trimethylsiloxy)silyl]propyl ally carbamate, or3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, ortrimethylsilylethyl vinyl carbonate, or trimethylsilylmethyl vinylcarbonate, or 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate(TRIS), or3-methaycryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane(SiGMA), or methyl di(trimethylsiloxy)silylpropylglycerolethylmethacrylate (SiGEMA), or monomethacryloxypropyl terminatedpolydimethylsiloxane (MCS-M11), MCR-M07, or monomethacryloxypropylterminated mono-n-butyl terminated polydimethyl siloxane (mPDMS), or anycombination thereof. In one example of a polymerizable composition ofthe present disclosure, the optional siloxane monomer can comprise afirst siloxane monomer and a second siloxane monomer, wherein the secondsiloxane monomer differs from the first siloxane present in thepolymerizable composition based on molecular weight, molecularstructure, or both molecular weight and structure. For example, theoptional second siloxane monomer or at least one third siloxane monomercan be a siloxane monomer of formula (1) having a different molecularweight than the first siloxane monomer of the polymerizable composition.In another example, the optional second siloxane monomer or at least onethird siloxane can comprise at least one of the siloxanes disclosed inthe following patents: US2007/0066706, US2008/0048350, U.S. Pat. No.3,808,178, U.S. Pat. No. 4,120,570, U.S. Pat. No. 4,136,250, U.S. Pat.No. 4,153,641, U.S. Pat. No. 470,533, U.S. Pat. No. 5,070,215, U.S. Pat.No. 5,998,498, U.S. Pat. No. 5,760,100, U.S. Pat. No. 6,367,929, andEP080539, the entire content of which are hereby incorporated byreference.

In another example of the present contact lenses, the optional siloxanemonomer can be a dual-end methacrylate end-capped polydimethylsiloxanehaving a number average molecular weight of at least 4,000 daltons. Itwill be understood that such siloxane monomers are bifunctional.

In one example of the present contact lenses, the optional siloxanemonomer can have a number average molecular weight of at least 4,000daltons, or at least 7,000 daltons, or at least 9,000 daltons, or atleast 11,000 daltons. The number average molecular weight of thesiloxane monomer can be less than 20,000 daltons. Thus, in somecontexts, the siloxane monomer can be considered a macromer, but it willbe referred to as a monomer herein since it forms a unit part of apolymer formed with the other reactive components of the polymerizablecomposition.

Examples of siloxane monomers can include monofunctional siloxanemonomers having at least one urethane linkage, such as the examples ofthe monofunctional siloxane monomers represented by formula (4):

where n of formula (4) is 0-30, or is 10-15. In a particular example,the siloxane monomer can be the monomer of formula (4) where n offormula (4) is 12-13 and having a molecular weight of about 1,500daltons. Examples of such monofunctional siloxane monomers described inU.S. Pat. No. 6,867,245, which is hereby incorporated by reference.

Examples of siloxane monomers can include bifunctional siloxane monomershaving at least two urethane linkages, such as the examples of thebifunctional siloxane monomers represented by formula (5):

wherein n of formula (5) is an integer of about 100-150, m of formula(5) is an integer of about 5 to about 10, and h is an integer of about 2to 8. Additional example of such bifunctional siloxane monomer, andmethods of making compounds of formula (5) are described in U.S. Pat.No. 6,867,245, which is hereby incorporated by reference. In aparticular example, the siloxane monomer can be a bifunctional siloxanemonomer having two urethane linkages and having a molecular weightgreater than 10,000 daltons, such as, for example, a molecular weight ofgreater than about 15,000 daltons.

The siloxane monomer can be a monofunctional siloxane monomerrepresented by formula (6):

wherein m of formula (6) represents one integer from 3 to 10, n offormula (6) represents one integer from 1 to 10, R¹ of formula (6) is analkyl group having from 1 to 4 carbon atoms, and each R² of formula (6)is independently either a hydrogen atom or a methyl group. In otherwords, on a single molecule of the siloxane monomer represented byformula 1, the first R² of formula (6), which is bonded to the CH₂ groupadjacent to the siloxane group, can be either a hydrogen atom or amethyl group, and the second R² of formula (6), which is bonded to the Cof the methacrylate end group, can also be either a hydrogen atom or amethyl group, regardless of whether the first R² of formula (6) is ahydrogen atom or a methyl group. In a particular example of the siloxanemonomer of formula (6), m of formula (6) is 4, n of formula (6) is 1, R¹of formula (6) is a butyl group, and each R² of formula (6) isindependently either a hydrogen atom or a methyl group. The molecularweight of the siloxane monomer of formula (6) can be less than 2,000daltons. In some examples, the molecular weight of the siloxane monomerof formula (6) is less than 1,000 daltons. Frequently, the molecularweight of the first siloxane monomer is from 400 to 700 daltons.Additional details of the siloxane monomer of formula (6) can beunderstood from US20090299022, the entire content of which is herebyincorporated by reference. As can be appreciated from formula (6), thefirst siloxane monomer has a single methacrylic functional end group.

The siloxane monomer can be a bifunctional siloxane monomer representedby formula (7):

wherein R₁ of formula (7) is selected from either hydrogen atom or amethyl group; R₂ of formula (7) is selected from either of hydrogen atomor a hydrocarbon group having 1 to 4 carbon atoms; m of formula (7)represents an integer of from 0 to 10; n of formula (7) represents aninteger of from 4 to 100; a and b represent integers of 1 or more; a+bis equal to 20-500; b/(a+b) is equal to 0.01-0.22; and the configurationof siloxane units includes a random configuration. In some examples inwhich the second siloxane monomer is a monomer represented by formula(7), m of formula (7) is 0, n of formula (7) is an integer from 5 to 15,a is an integer from 65 to 90, b is an integer from 1 to 10, R₁ offormula (7) is a methyl group, and R₂ of formula (7) is either ahydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Oneexample of such a second siloxane monomer as represented by formula (7)is abbreviated Si2 in the examples. In certain examples, the numberaverage molecular weight for this second siloxane monomer represented byformula (7) is from about 9,000 daltons to about 10,000 daltons. Inother examples, the second siloxane monomer represented by formula (7)is from about 5,000 daltons to about 10,000 daltons. It can beappreciated that the second siloxane represented by formula (7) is abifunctional siloxane having two terminal methacrylic groups. Additionaldetails of this second siloxane monomer can be found in US20090234089,the entire content of which is incorporated herein by reference.

The siloxane monomer can be a bifunctional siloxane monomer representedby formula (8):

wherein R³ is selected from either hydrogen atom or a methyl group, m offormula (8) represents an integer from 0 to 15, and n of formula (8)represents an integer from 1 to 500. In one example, the siloxanemonomer is represented by formula (8), and R³ is a methyl group, m offormula (8) is 0, and n of formula (8) is one integer from 40 to 60.

In another example, the siloxane monomer can be a bifunctional siloxanemonomer represented by formula (9), and is abbreviated Si3 in theexamples (available from Gelest, Inc., Morrisville, Pa. as product codeDMS-R18):

In certain examples, the siloxane of formula (9) has a number averagemolecular weight of about 4,000 to about 4,500 daltons.

In certain examples, the polymerizable composition can also comprise asecond siloxane monomer. The second siloxane monomer can have more thanone functional group, or can have a number average molecular weight ofat least 3,000 daltons, or can have both more than one functional groupand a number average molecular weight of at least 3,000 daltons. If thesecond siloxane monomer has two functional groups, such as twomethacrylate groups, it is a bifunctional monomer. If the secondsiloxane monomer has three functional groups, it is a trifunctionalmonomer.

When the polymerizable composition comprises a first siloxane and asecond siloxane, the first siloxane monomer and the second siloxanemonomer can be present in amounts such that the ratio of the firstsiloxane monomer to the second siloxane monomer is at least 1:1 based onunit parts, or is at least 2:1 based on unit parts. For example, thefirst siloxane monomer and the second siloxane monomer can be present inthe polymerizable composition in a ratio from about 2:1 to about 10:1based on unit parts. In another example, the first siloxane monomer andthe second siloxane monomer can be present in the polymerizablecomposition in a ratio from about 3:1 to about 6:1 based on unit parts.In one example, the first siloxane monomer and the second siloxanemonomer can be present in the polymerizable composition in a ratio ofabout 4:1 based on unit parts.

When the polymerizable composition comprises at least one siloxanemonomer, the total amount of siloxane monomers present in thepolymerizable composition (e.g., the sum of the unit parts of theoptional first siloxane monomer, the optional second siloxane monomer,and any other optional siloxane monomers present in the polymerizablecomposition) can be from about 10 to about 60 unit parts, or from about25 to about 50 unit parts, or from about 35 to about 40 unit parts.

In one particular example, when the siloxane monomer component comprisesa combination of at least two siloxane monomers each having a differentmolecular weight, the molecular weight of the first siloxane monomer canbe less than 2,000 daltons. In some examples, the molecular weight ofthe first siloxane monomer can be less than 1,000 daltons. Frequently,the molecular weight of the first siloxane monomer is from 400 to 700daltons.

When the at least one siloxane monomer is present in the polymerizablecomposition, as previously discussed, the at least one siloxane monomercan comprise a first siloxane monomer and a second siloxane monomer. Inone example, the first siloxane monomer can consist of a siloxanemonomer of formula (5) and the second siloxane monomer can consist of asiloxane monomer of formula (4). In another example, the first siloxanemonomer can consist of a siloxane monomer of formula (4), and the secondsiloxane monomer con consist of a siloxane monomer of formula (5). Inanother example, the first siloxane monomer can consist of a siloxanemonomer of formula (6), and the second siloxane can consist of asiloxane monomer of formula (7). In another example, the first siloxanemonomer can consist of a siloxane monomer of formula (7), and the secondsiloxane monomer can consist of a siloxane monomer of formula (6). Inanother example, the first siloxane monomer can consist of a siloxanemonomer of formula (4), and the second siloxane monomer can consist of asiloxane monomer of formula (7). In yet another example, the firstsiloxane monomer can consist of a siloxane monomer of formula (7), andthe second siloxane monomer can consist of a siloxane monomer of formula(4). In any or all of the examples described herein, the siloxanemonomer component can comprise a third siloxane monomer. For example,the third siloxane monomer can consist of a siloxane monomer of formula(8).

Optionally, the polymerizable compositions of the present disclosure canoptionally comprise at least one non-silicon hydrophobic monomer. Thehydrophobic monomer is understood to be a non-silicone polymerizableingredient having only one polymerizable functional group present in itsmolecular structure. The at least one hydrophobic monomer of thepolymerizable composition can be one hydrophobic monomer, or cancomprise a hydrophobic monomer component composed of at least twohydrophobic monomers. Examples of hydrophobic monomers that can be usedin the polymerizable compositions disclosed herein, include, withoutlimitation, acrylate-containing hydrophobic monomers, ormethacrylate-containing hydrophobic monomers, or any combinationthereof. Examples of hydrophobic monomers include, without limitation,methyl acrylate, or ethyl acrylate, or propyl acrylate, or isopropylacrylate, or cyclohexyl acrylate, or 2-ethylhexyl acrylate, or methylmethacrylate (MMA), or ethyl methacrylate, or propyl methacrylate, orbutyl acrylate, or vinyl acetate, or vinyl propionate, or vinylbutyrate, or vinyl valerate, or styrene, or chloroprene, or vinylchloride, or vinylidene chloride, or acrylonitrile, or 1-butene, orbutadiene, or methacrylonitrile, or vinyltoluene, or vinyl ethyl ether,or perfluorohexylethylthiocarbonylaminoethyl methacrylate, or isobornylmethacrylate, or trifluoroethyl methacrylate, or hexafluoroisopropylmethacrylate, or hexafluorobutyl methacrylate, or ethylene glycol methylether methacrylate (EGMA), or any combination thereof. In one particularexample, the hydrophobic monomer or monomer component can comprise orconsist of MMA, or EGMA, or both.

When present in the polymerizable composition, the hydrophobic monomeror monomer component can be present in an amount from about 5 to about25 unit parts, or from about 10 to about 20 unit parts.

In one example, the hydrophobic monomer component can comprise at leasttwo hydrophobic monomers each having different polymerizable functionalgroups. In another example, the hydrophobic monomer component cancomprise at least two hydrophobic monomers each having the samepolymerizable functional group. The hydrophobic monomer component cancomprise or consist of two hydrophobic monomers, both having the samepolymerizable functional group. In one example, the hydrophobic monomercomponent can comprise or consist of two hydrophobicmethacrylate-containing monomers. The hydrophobic monomer component cancomprise or consist of MMA and EGMA. In one example, the at least twohydrophobic monomers of the hydrophobic monomer component can compriseor consist of MMA and EGMA, and the ratio of the unit parts of MMA tothe unit parts of EGMA present in the polymerizable composition can befrom about 6:1 to about 1:1. The ratio of the unit parts of MMA and EGMApresent in the polymerizable composition can be about 2:1 based on theunit parts of MMA to the unit parts of EGMA.

In accordance with the present disclosure, a cross-linking agent isunderstood to be a monomer having more than one polymerizable functionalgroup as part of its molecular structure, such as two or three or fourpolymerizable functional groups, i.e., a multifunctional monomer such asa bifunctional or trifunctional or tetrafunctional monomer. Non-siliconcross-linking agents that can be used in the polymerizable compositionsdisclosed herein include, for example, without limitation, allyl(meth)acrylate, or lower alkylene glycol di(meth)acrylate, or poly(loweralkylene)glycol di(meth)acrylate, or lower alkylene di(meth)acrylate, ordivinyl ether, or divinyl sulfone, or di- and trivinylbenzene, ortrimethylolpropane tri(meth)acrylate, or pentaerythritoltetra(meth)acrylate, or bisphenol A di(meth)acrylate, ormethylenebis(meth)acrylamide, or triallyl phthalate and diallylphthalate, or any combination thereof. Cross-linking agents, asdisclosed in Examples 1-37, include, for example, ethylene glycoldimethacrylate (EGDMA), or triethylene glycol dimethacrylate (TEGDMA),or triethylene glycol divinyl ether (TEGDVE), or any combinationthereof. In one example, the cross-linking agent can have a molecularweight less than 1500 daltons, or less than 1000 daltons, or less than500 daltons, or less than 200 daltons.

In one example, the cross-linking agent or cross-linking agent componentcan comprise or consist of a vinyl-containing cross-linking agent. Asused herein, a vinyl-containing cross-linking agent is a monomer havingat least two polymerizable carbon-carbon double bonds (i.e., at leasttwo vinyl polymerizable functional groups) present in its molecularstructure, where each of the at least two polymerizable carbon-carbondouble bonds present in the vinyl polymerizable functional groups of thevinyl-containing cross-linking agent is less reactive than acarbon-carbon double bond present in an acrylate or methacrylatepolymerizable functional group. Although carbon-carbon double bonds arepresent in acrylate and methacrylate polymerizable functional groups, asunderstood herein, cross-linking agents comprising one or more acrylateor methacrylate polymerizable group (e.g., an acrylate-containingcross-linking agent or a methacrylate-containing cross-linking agent)are not considered to be vinyl-containing cross-linking agents.Polymerizable functional groups having carbon-carbon double bonds whichare less reactive than the carbon-carbon double bonds of acrylate ormethacrylate polymerizable groups include, for example, vinyl amide,vinyl ester, vinyl ether and allyl ester polymerizable functionalgroups. Thus, as used herein, vinyl-containing cross-linking agentsinclude, for example, cross-linking agents having at least twopolymerizable functional groups selected from a vinyl amide, a vinylether, a vinyl ester, an allyl ester, and any combination thereof. Asused herein, a mixed vinyl-containing cross-linking agent is across-linking agent having at least one polymerizable carbon-carbondouble bond (i.e., at least one vinyl polymerizable functional group)present in its structure which is less reactive than the carbon-carbondouble bond present in an acrylate or methacrylate polymerizablefunctional group, and at least one polymerizable functional grouppresent in its structure having a carbon-carbon double bond which is atleast as reactive as the carbon-carbon double bond in an acrylate ormethacrylate polymerizable functional group.

When present in the polymerizable composition, the vinyl-containingcross-linking agent or cross-linking agent component can be present inan amount from about 0.01 unit parts to from about 2.0 unit parts, orfrom about 0.01 unit parts to about 0.80 unit parts, or from about 0.01unit parts to about 0.30 unit parts, or from about 0.05 unit parts toabout 0.20 unit parts, or in an amount of about 0.1 unit parts.

In one example, the cross-linking agent or cross-linking agent componentcan comprise or consist of a non-vinyl-containing cross-linking agent,i.e., a cross-linking agent which is not a vinyl-containingcross-linking agent. For example, the non-vinyl-containing cross-linkingagent or cross-linking agent component can comprise or consist of anacrylate-containing cross-linking agent (i.e., a cross-linking agenthaving at least two acrylate polymerizable functional groups), or amethacrylate-containing cross-linking agent (i.e., at least twomethacrylate polymerizable functional groups), or at least oneacrylate-containing cross-linking agent and at least onemethacrylate-containing cross-linking agent.

When present in the polymerizable composition, the non-vinylcross-linking agent or cross-linking agent can be present in an amountfrom about 0.01 unit parts to about 5 unit parts, or from about 0.1 unitparts to about 4 unit parts, or from about 0.3 unit parts to about 3.0unit parts, or from about 0.2 unit parts to about 2.0 unit parts.

The cross-linking agent component can comprise or consist of acombination of two or more cross-linking agents, each of which has adifferent polymerizable functional group. For example, the cross-linkingagent component can comprise one vinyl-containing cross-linking agent,and one acrylate-containing cross-linking agent. The cross-linking agentcomponent can comprise one vinyl-containing cross-linking agent and onemethacrylate-containing cross-linking group. The cross-linking agentcomponent can comprise or consist of one vinyl ether-containingcross-linking agent, and one methacrylate-containing cross-linkingagent.

When the polymerizable composition comprises at least one cross-linkingagent, the total amount of cross-linking agents (i.e., the total unitparts of all cross-linking agents present in the polymerizablecomposition) can be an amount from about 0.01 unit parts to about 5 unitparts, or from about 0.1 unit parts to about 4 unit parts, or from about0.3 unit parts to about 3.0 unit parts, or from about 0.2 unit parts toabout 2.0 unit parts, or from about 0.6 to about 1.5 unit parts.

In one example, when the present polymerizable composition comprises atleast one vinyl-containing crosslinking agent, the total amount ofvinyl-containing cross-linking agents present in the polymerizablecomposition can be an amount from about 0.01 unit parts to from about2.0 unit parts, or from about 0.01 unit parts to about 0.80 unit parts,or from about 0.01 unit parts to about 0.30 unit parts, or from about0.05 unit parts to about 0.20 unit parts, or in an amount of about 0.1unit parts.

When the polymerizable composition comprises a first siloxane monomerand at least one cross-linking agent, the first siloxane monomer (e.g.,a first siloxane monomer present as the only siloxane monomer of thepolymerizable composition, or a first siloxane monomer present as partof a siloxane monomer component comprised of two or more siloxanemonomers) and the at least one cross-linking agent (i.e., a singlecross-linking agent or a cross-linking agent component composed of twoor more cross-linking agents) can be present in the polymerizablecomposition in a ratio of at least 10:1 based on the total unit parts byweight of the first siloxane monomer to the total unit parts by weightof the at least one cross-linking agent (i.e., the sum of the unit partsof all vinyl-containing cross-linking agents present in thepolymerizable composition). For example, the ratio can be at least 25:1or at least 50:1 or at least 100:1 based on unit parts by weight.

In one example, the at least one cross-linking agent can comprise atleast one vinyl-containing cross-linking agent, and at least onemethacrylate-containing cross-linking agent. In another example, the atleast one cross-linking agent can consist of only one or morevinyl-containing cross linking agents. In another example, the at leastone cross-linking agent can comprise or consist of at least one vinylether-containing cross-linking agent. In yet another example, the atleast one cross-linking agent can consist of only one or morevinyl-containing cross linking agents. In one particular example, the atleast one cross-linking agent can comprise or consist of at least onevinyl ether-containing cross-linking agent.

When the at least one cross-linking agent comprises or consists of atleast one vinyl-containing cross-linking agent (i.e., a singlevinyl-containing cross-linking agent or a vinyl-containing cross-linkingagent component composed of two or more vinyl-containing cross-linkingagents), the first siloxane monomer and the at least onevinyl-containing cross-linking agent can be present in the polymerizablecomposition in a ratio of at least about 50:1 based on a ratio of atotal number of unit parts of the first siloxane monomer to a totalnumber of unit parts of the least one vinyl-containing cross-linkingagent (i.e., the sum of the unit parts of all vinyl-containingcross-linking agents present in the polymerizable composition). Forexample, the ratio can be from about 50:1 to about 500:1, or from about100:1 to about 400:1, or from about 200:1 to about 300:1 based on unitparts by weight.

When the polymerizable composition comprises a first siloxane monomerand at least one additional siloxane monomer (i.e., a second siloxane,and optionally a third siloxane monomer, a fourth siloxane monomer,etc.) in combination with at least one cross-linking agent, the siloxanemonomers and the at least one vinyl-containing monomer can be present inthe polymerizable composition in a ratio of at least about 100:1 basedon a ratio of a total number of unit parts of the each siloxane monomerpresent in the polymerizable composition (i.e., the sum of the unitparts of the first siloxane and the second siloxane monomer and, ifpresent, the third siloxane monomer, etc.) to a total number of unitparts of the least one vinyl-containing cross-linking agent (i.e., thesum of the unit parts of all vinyl-containing cross-linking agentspresent in the polymerizable composition). For example, the ratio can befrom about 50:1 to about 500:1, or from about 100:1 to about 400:1, orfrom about 200:1 to about 300:1 based on unit parts by weight.

In one example, a total amount of siloxane monomers present in thepolymerizable composition (i.e., the total unit parts of the firstsiloxane monomer, and, if present, a second siloxane monomer, and an atleast one third siloxane monomer) can be an amount from about 30 to 45unit parts, or from about 36 to 40 unit parts.

The polymerizable composition can optionally include one or more organicdiluents, one or more polymerization initiators (i.e., ultraviolet (UV)initiators or thermal initiators, or both), or one or more UV absorbingagents, or one or more tinting agents, or one or more oxygen scavengers,or one or more chain transfer agents, or any combination thereof. Theseoptional ingredients can be polymerizable or non-polymerizableingredients. In one example, the polymerizable compositions can bediluent-free in that they do not contain any organic diluent to achievemiscibility between the siloxanes and the other lens formingingredients, such as the optional hydrophilic monomers, hydrophobicmonomer, and cross-linking agents. In addition, many of the presentpolymerizable compositions are essentially free of water (e.g., containno more than 3.0% or 2.0% water by weight).

The polymerizable compositions disclosed herein can optionally compriseone or more organic diluents, i.e., the polymerizable composition cancomprise an organic diluent, or can comprise an organic diluentcomponent comprising two or more organic diluents. Organic diluents thatcan optionally be included in the present polymerizable compositionsinclude alcohols, including lower alcohols, such as, for example,without limitation, pentanol, or hexanol, or octanol, or decanol, or anycombination thereof. When included, the organic diluent or organicdiluent component can be provided in the polymerizable composition in anamount from about 1 to about 70 unit parts, or from about 2 unit partsto about 50 unit parts, or from about 5 unit parts to about 30 unitparts.

The present polymerizable compositions can optionally comprise one ormore polymerization initiators, i.e., the polymerizable composition cancomprise an initiator, or can comprise an initiator component comprisingtwo or more polymerization initiators. Polymerization initiators thatcan be included in the present polymerizable compositions include, forexample, azo compounds, or organic peroxides, or both. Initiators thatcan be present in the polymerizable composition include, for example,without limitation, benzoin ethyl ether, or benzyl dimethyl ketal, oralpha, alpha-diethoxyacetophenone, or 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or benzoin peroxide, or t-butyl peroxide, orazobisisobutyronitorile, or azobisdimethylvaleronitorile, or anycombination thereof. UV photoinitiators can include, for example,phosphine oxides such as diphenyl (2,4,6-trimethyl benzoyl) phosphineoxide, or benzoin methyl ether, or 1-hydroxycyclohexylphenyl ketone, orDarocur (available from BASF, Florham Park, N.J., USA), or Irgacur (alsoavailable from BASF), or any combination thereof. In many of Examples1-37 disclosed herein, the polymerization initiator is the thermalinitiator 2,2′-azobis-2-methyl propanenitrile (VAZO-64 from E.I. DuPontde Nemours & Co., Wilmington, Del., USA). Other commonly usedthermoinitiators can include 2,2′-azobis(2,4-dimethylpentanenitrile)(VAZO-52) and 1,1′-azo bis(cyanocyclohexane) (VAZO-88). Thepolymerization initiator or initiator component can be present in thepolymerizable composition in an amount from about 0.01 unit parts toabout 2.0 unit parts, or in an amount from about 0.1 unit parts to about1.0 unit parts, or from about 0.2 unit parts to about 0.6 unit parts byweight.

Optionally, the present polymerizable compositions can comprise one ormore UV absorbing agents, i.e., the polymerizable composition cancomprise an UV absorbing agent, or can comprise an UV absorbing agentcomponent comprising two or more UV absorbing agents. UV absorbingagents that can be included in the present polymerizable compositionsinclude, for example, benzophenones, or benzotriazoles, or anycombination thereof. In many of Examples 1-37 disclosed herein, the UVabsorbing agent is 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate (UV-416)or 2-(3-(2H-benzotriazol-2-YL)-4-hydroxy-phenyl)ethyl methacrylate(NORBLOC 7966 from Noramco, Athens, Ga., USA). The UV absorbing agent orUV absorbing agent component can be present in the polymerizablecomposition in an amount from about 0.01 unit parts to about 5.0 unitparts, or in an amount from about 0.1 unit parts to about 3.0 unitparts, or from about 0.2 unit parts to about 2.0 unit parts by weight.

The polymerizable compositions of the present disclosure can alsooptionally include at least one tinting agent (i.e., one tinting agentor a tinting agent component comprising two or more tinting agents),although both tinted and clear lens products are contemplated. In oneexample, the tinting agent can be a reactive dye or pigment effective toprovide color to the resulting lens product. The tinting agent ortinting agent component of the polymerizable composition can comprise apolymerizable tinting agent, or can comprise a non-polymerizable tintingagent, or any combination thereof. The polymerizable tinting agent canbe a tinting agent whose molecular structure comprises a polymerizablefunctional group, or can be a tinting agent whose molecular structureincludes both a monomer portion and a dye portion, i.e., the tintingagent can be a monomer-dye compound. The molecular structure of thetinting agent can comprise a beta sulfone functional group, or cancomprise a triazine functional group. Tinting agents can include, forexample, VAT Blue 6(7,16-Dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone), or1-Amino-4-[3-(beta-sulfatoethylsulfonyl)anilio]-2-anthraquinonesulfonicacid (C. I. Reactive Blue 19, RB-19), or a monomer-dye compound ofReactive Blue 19 and hydroxyethylmethacrylate (RB-19 HEMA), or1,4-bis[4-[(2-methacryl-oxyethyl)phenylamino]anthraquinone (ReactiveBlue 246, RB-246, available from Arran Chemical Company, Athlone,Ireland), or 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedionebis(2-propenoic)ester (RB-247), or Reactive Blue 4, RB-4, or amonomer-dye compound of Reactive Blue 4 and hydroxyethyl methacrylate(RB-4 HEMA or “Blue HEMA”), or any combination thereof. In one example,the tinting agent or tinting agent component can comprise apolymerizable tinting agent. The polymerizable tinting agent componentcan comprise, for example, RB-246, or RB-274, or RB-4 HEMA, or RB-19HEMA, or any combination thereof. Examples of monomer-dye compoundsinclude RB-4 HEMA and RB-19 HEMA. Additional examples of monomer-dyecompounds are described in U.S. Pat. No. 5,944,853 and U.S. Pat. No.7,216,975, both of which are incorporated in their entirety by referenceherein. Other exemplary tinting agents are disclosed, for example, inU.S. Patent Application Publication No. 2008/0048350, the disclosure ofwhich is incorporated in its entirety herein by reference. In many ofExamples 1-37 disclosed herein, the tinting agent is a reactive bluedye, such as those described in U.S. Pat. No. 4,997,897, the disclosureof which is incorporated in its entirety herein by reference. Othersuitable tinting agents for use in accordance with the present inventionare phthalocyanine pigments such as phthalocyanine blue, orphthalocyanine green, or chromic-alumina-cobaltous oxide, or chromiumoxides, or various iron oxides for red, yellow, brown and black colors,or any combination thereof. Opaquing agents such as titanium dioxide canalso be incorporated. For certain applications, a combination of tintingagents having different colors can be employed as the tinting agentcomponent. If employed, the tinting agent or tinting agent component canbe present in the polymerizable composition in an amount ranging fromabout 0.001 unit parts to about 15.0 unit parts, or about 0.005 unitparts to about 10.0 unit parts, or about 0.01 unit parts to about 8.0unit parts.

Chain transfer is a polymerization reaction in which the activity of agrowing polymer chain is transferred to another molecule, reducing theaverage molecular weight of the final polymer. The polymerizablecompositions of the present disclosure can optionally comprise at leastone chain transfer agent, i.e., can comprise one chain transfer agent orcan comprise a chain transfer agent component comprising at least twochain transfer agents. Examples of chain transfer agents which can beincluded as the chain transfer agent or the chain transfer component ofthe present polymerizable compositions include, for example, thiolcompounds, or halocarbon compounds, or C3-C5 hydrocarbons, or anycombination thereof. In many of Examples 1-37 disclosed herein, thechain transfer agent is allyloxy ethanol. When present in thepolymerizable composition, the chain transfer agent or chain transferagent component can be present in an amount from about 0.01 unit partsto about 1.5 unit parts, for example from about 0.1 unit parts to about0.5 unit parts.

Various methods of measuring contact angles are known to those ofordinary skill in the art, including the captive bubble method. Thecontact angle can be a static or dynamic contact angle.

Silicone hydrogel contact lenses of the present invention can havecaptive bubble dynamic advancing contact angles of less than 120degrees, such as, for example, less than 90 degrees when fully hydrated,less than 80 degrees when fully hydrated, less than 70 degrees whenfully hydrated, or less than 65 degrees when fully hydrated, or lessthan 60 degrees when fully hydrated, or less than 50 degrees when fullyhydrated.

Silicone hydrogel contact lenses of the present invention can havecaptive bubble static contact angles of less than 70 degrees when fullyhydrated, or less than 60 degrees when fully hydrated, or less than 55degrees when fully hydrated, or less than 50 degrees when fullyhydrated, or less than 45 degrees when fully hydrated.

In accordance with the present disclosure, the silicone hydrogel contactlenses can have, when fully hydrated, equilibrium water contents (EWC)sfrom about 30 to about 70%. For example, the contact lenses can have anEWC from about 45% to about 65%, or from about 50% to about 63%, or fromabout 50% to about 67%, or from about 55% to about 65% by weight whenfully hydrated. Methods of determining EWC are known to those ofordinary skill in the art, and can be based on weight loss from a lensduring a drying process.

The present contact lenses can have an oxygen permeability (or Dk) of atleast 55 barrers (Dk≧55 barrers), or an oxygen permeability of at least60 barrers (Dk≧60 barrers), or an oxygen permeability of at least 65barrers (Dk≧65 barrers). The lenses can have an oxygen permeability fromabout 55 barrers to about 135 barrers, or from about 60 barrers to about120 barrers, or from about 65 barrers to about 90 barrers, or from about50 barrers to about 75 barrers. Various methods of determining oxygenpermeability are known to those of ordinary skill in the art.

The present contact lenses can have an oxygen permeability of at least55 barrers (Dk≧55 barrers), or an EWC from about 30% to about 70%, or acaptive bubble dynamic advancing contact angle less than 90 degrees, ora captive bubble static contact angle less than 70 degrees, or anycombination thereof. In one example, the contact lenses can have anoxygen permeability of at least 60 barrers (Dk≧60 barrers), or an EWCfrom about 35% to about 65%, or a captive bubble dynamic advancingcontact angle less than 70 degrees, or a captive bubble static contactangle less than 55 degrees, or any combination thereof. In anotherexample, the present contact lenses can have an oxygen permeability ofat least 65 barrers, or an EWC from about 45% to about 65%, or a captivebubble dynamic advancing contact angle less than 70 degrees, or acaptive bubble static contact angle less than 55 degrees, or anycombination thereof.

In one example, the present contact lenses have an oxygen permeabilityof at least 55 barrers, an EWC from about 30% to about 70%, a captivebubble dynamic advancing contact angle less than 70 degrees, and acaptive bubble static contact angle less than 55 degrees.

In one example, the present contact lenses can have, when fullyhydrated, an oxygen permeability of at least 55 barrers (Dk≧55 barrers),and a tensile modulus from about 0.2 MPa to about 0.9 MPa, and a captivebubble dynamic advancing contact angle less than 70 degrees, and acaptive bubble static contact angle less than 55 degrees.

The silicone hydrogel contact lenses of the present disclosure can have,when fully hydrated, an average tensile modulus about 0.20 MPa to about0.90 MPa. For example, the average modulus can be from about 0.30 MPa toabout 0.80 MPa, or from about 0.40 MPa to about 0.75 MPa, or from about0.50 MPa to about 0.70 MPa.

As used herein, the modulus of a contact lens or lens body is understoodto refer to the tensile modulus, also know as Young's modulus. It is ameasure of the stiffness of an elastic material. The tensile modulus canbe measured using a method in accordance with ANSI Z80.20 standard. Inone example, the tensile modulus can be measured using an Instron Model3342 or Model 3343 mechanical testing system.

The silicone hydrogel contact lenses of the present disclosure can have,when fully hydrated, an average percentage of energy loss from about 25%to about 40%. For example, the average percentage of energy loss can befrom about 27% to about 40%, or can be from about 30% to about 37%.

As used herein, percentage of energy loss is a measure of the energylost as heat when energy loading and unloading cycles are applied toviscoelastic materials. Percentage of energy loss can be determinedusing a number of methods known to those of ordinary skill in the art.For example, the force involved in stretching a sample to 100% strain,and then returning it to 0% at a constant rate can be determined andused to calculate the percentage energy loss for the material.

The present contact lenses, when fully hydrated, can have an ionofluxless than about 8.0×10⁻³ mm²/min, or less than about 7.0×10⁻³ mm²/min,or less than about 5.0×10⁻³ mm²/min. Various methods of determiningionoflux are conventional and are known to those of ordinary skill inthe art.

In one example, the present contact lenses can have a wet extractablecomponent. The wet extractable component is determined based on theweight lost during methanol extraction of contact lenses which have beenfully hydrated and sterilized prior to drying and extraction testing.The wet extractable component can comprise unreacted or partiallyreacted polymerizable ingredients of the polymerizable composition. Thewet extractable component consists of organic solvent-extractablematerials remaining in the lens body after the lens body has been fullyprocessed to form a sterilized contact lens, for lenses formed frompolymerizable compositions comprising non-polymerizable ingredients. Forlenses extracted during manufacturing in either an extraction liquidcomprising a volatile organic solvent or an extraction liquid free of anorganic solvent, in most cases, substantially all of thenon-polymerizable ingredients will have been removed from the lens body,and so the wet extractable component may consist essentially ofextractable components formed from reactive polymerizable ingredients ofthe polymerizable composition, i.e., unreacted polymerizable componentsand partially reacted polymerizable ingredients. In lenses made from apolymerizable composition free of a diluent, the wet extractablecomponent can be present in the contact lens in an amount from about 1%wt/wt to about 15% wt/wt, or from about 2% wt/wt to about 10% wt/wt, orfrom about 3% wt/wt to about 8% wt/wt based on the dry weight of thelens body prior to extraction testing. In lenses made from apolymerizable composition comprising a diluent, the wet extractablecomponent may consist of a portion of the diluent as well as unreactedand partially reacted polymerizable ingredients, and can be present inthe contact lens in an amount from about 1% wt/wt to about 20% wt/wt, orfrom about 2% wt/wt to about 15% wt/wt of the lens, or from about 3%wt/wt to about 10% wt/wt based on the dry weight of the lens body priorto extraction testing.

In one example, the present contact lenses have a dry extractablecomponent. The dry extractable component is determined based on theweight lost during extraction in methanol of polymeric lens bodies whichhave not been washed, extracted (as part of a manufacturing process),hydrated or sterilized prior to the drying and extraction testing. Thedry extractable component can comprise unreacted or partially reactedpolymerizable ingredients of the polymerizable composition. Whenoptional non-polymerizable ingredients such as diluents and the like arepresent in the polymerizable composition, the dry extractable componentmay further comprise the non-polymerizable ingredients.

In lenses made from a polymerizable composition free of a diluent, thedry extractable component of the lens consists primarily of dryextractable components contributed by polymerizable ingredients of thepolymerizable composition (i.e., unreacted or partially reactedpolymerizable ingredients), and may also include dry extractablematerials contributed by optional non-polymerizable components presentin the polymerizable composition in small amounts (e.g., less than 3%wt/wt), such as, for example, tinting agents, oxygen scavengers, and thelike. In lenses made from a polymerizable composition free of a diluent,the dry extractable component can be present in the polymeric lens bodyin an amount from about 1% wt/wt to about 30% wt/wt of the lens body, orfrom about 2% wt/wt to about 25% wt/wt, or from about 3% wt/wt to about20% wt/wt, or from about 4% wt/wt to about 15% wt/wt, or from 2% wt/wtto less than 10% wt/wt based on the dry weight of the lens body prior toextraction testing.

In lenses made from a polymerizable composition comprising a largeamount (e.g., more than 3% wt/wt) of an optional non-polymerizableingredient such as a diluent, the dry extractable component consists ofextractable materials contributed by reactive ingredients as well asextractable components contributed by non-polymerizable ingredients ofthe polymerizable composition. The total amount of dry extractablecomponents contributed by reactive ingredients and non-polymerizableingredients present in the contact lens can consist of an amount fromabout 1% wt/wt to about 75% wt/wt, or from about 2% wt/wt to about 50%wt/wt of the lens, or from about 3% wt/wt to about 40% wt/wt, or fromabout 4% wt/wt to about 20% wt/wt, or from about 5% to about 10% basedon the dry weight of the polymeric lens body prior to extractiontesting. The total amount of dry extractable components contributed bypolymerizable ingredients (i.e., unreacted or partially reactedpolymerizable ingredients) can be an amount from about 1% wt/wt to about30% wt/wt of the lens body, or from about 2% wt/wt to about 25% wt/wt,or from about 3% wt/wt to about 20% wt/wt, or from about 4% wt/wt toabout 15% wt/wt, or from 2% wt/wt to less than 10% wt/wt based on thedry weight of the lens body prior to extraction testing.

It is also to be understood that reference to the contact lens formedfrom the compositions described herein is a lens body with an anteriorsurface and a posterior surface, the posterior surface being configuredto be placed in contact with the cornea of an eye of a contact lenswearer. The lens body of the present invention can be entirelytransparent. Alternatively, when the contact lens is a cosmetic lensconfigured to alter the appearance of an iris of a contact lens wearer,the lens body can comprise a transparent optic zone.

This invention is useful for contact lenses which, when worn, can be incontact with epithelial tissue or other eye tissues. This invention isuseful for all known types of contact lenses, including both soft andrigid lens materials. In an example of the contact lens of the presentinvention, the contact lens is a lens with at least one optic zoneconfigured to provide vision correction, to improve visual acuity, or toboth provide vision correction and improve visual acuity. For example,the optic zone can be configured to provide a spherical correction, atoric correction, or a third order or higher correction. The optic zonecan be configured to improve visual acuity at near viewing distances, atfar viewing distances, or at both near and far viewing distances. Otherfeatures and examples of the contact lenses of the present invention areillustrated in the following sections.

The present hydrogel contact lenses are vision correcting or visionenhancing contact lenses. The lenses may be spheric lenses or asphericlenses. The lenses may be monofocal lenses or multifocal lenses,including bifocal lenses. In certain examples, the present lenses arerotationally stabilized lenses, such as a rotationally stabilized toriccontact lens. A rotationally stabilized contact lens may be a contactlens that comprises a lens body that includes a ballast. For example,the lens body may have a prism ballast, a periballast, and/or one ormore thinned superior and inferior regions.

The present lenses also comprise lens bodies that include a peripheraledge region. The peripheral edge region may include a rounded portion.For example, the peripheral edge region may comprise a rounded posterioredge surface, a rounded anterior edge surface, or a combination thereof.The peripheral edge can be completely rounded from the anterior surfaceto the posterior surface. Therefore, it can be understood that the lensbody of the present lenses may comprise a rounded peripheral edge.

The contact lenses of the present disclosure, as they are configured tobe placed or disposed on a cornea of an animal or human eye, areophthalmically acceptable contact lenses. As used herein, anophthalmically acceptable contact lens is understood to be a contactlens having at least one of a number of different properties asdescribed below. An ophthalmically acceptable contact lens can be formedof, and packaged in, ophthalmically acceptable ingredients such that thelens is not cytotoxic and does not release irritating and/or toxicingredients during wear. An ophthalmically acceptable contact lens canhave a level of clarity in the optic zone of the lens (i.e., the portionof the lens providing vision correction) sufficient for its intended usein contact with the cornea of an eye, for example, a transmittance of atleast 80%, or at least 90%, or at least 95% of visible light. Anophthalmically acceptable contact lens can have sufficient mechanicalproperties to facilitate lens handling and care for a duration of timebased on its intended lifetime. For example, its modulus, tensilestrength, and elongation can be sufficient to withstand insertion, wear,removal and, optionally, cleaning over the intended lifetime of thelens. The level of these properties which are appropriate will varydepending upon the intended lifetime and usage of the lens (e.g., singleuse daily disposable, multiple use monthly, etc). An ophthalmicallyacceptable contact lens can have an effective or appropriate ionoflux tosubstantially inhibit or substantially prevent corneal staining, such ascorneal staining more severe than superficial or moderate cornealstaining after continuous wear of the lens on a cornea for 8 or morehours. An ophthalmically acceptable contact lens can have a level ofoxygen permeability sufficient to allow oxygen to reach the cornea of aneye wearing the lens in an amount sufficient for long term cornealhealth. An ophthalmically acceptable contact lens can be a lens whichdoes not cause substantial or undue corneal swelling in an eye wearingthe lens, for example, no more than about 5% or 10% corneal swellingafter being worn on a cornea of an eye during an overnight sleep. Anophthalmically acceptable contact lens can be a lens which allowsmovement of the lens on the cornea of an eye wearing the lens sufficientto facilitate tear flow between the lens and the eye, in other words,does not cause the lens to adhere to the eye with sufficient force toprevent normal lens movement, and that has a low enough level ofmovement on the eye to allow vision correction. An ophthalmicallyacceptable contact lens can be a lens which allows wearing of the lenson the eye without undue or significant discomfort and/or irritationand/or pain. An ophthalmically acceptable contact lens can be a lenswhich inhibits or substantially prevents lipid and/or protein depositionsufficient to cause the lens wearer to remove the lens because of suchdeposits. An ophthalmically acceptable contact lens can have at leastone of a water content, or a surface wettability, or a modulus or adesign, or any combination thereof, that is effective to facilitateophthalmically compatible wearing of the contact lens by a contact lenswearer at least for one day. Ophthalmically compatible wearing isunderstood to refer to the wearing of a lens by a lens wearer withlittle or no discomfort, and with little or no occurrence of cornealstaining. Determining whether a contact lens is ophthalmicallyacceptable can be achieved using conventional clinical methods, such asthose performed by an eye care practitioner, and as understood bypersons of ordinary skill in the art.

In one example of the present disclosure, the contact lens can haveophthalmically acceptably wettable lens surfaces. For example, thecontact lens can have the ophthalmically acceptably wettable lenssurfaces when the polymerizable composition used to form the polymericlens body is free of an internal wetting agent, or when thepolymerizable composition used to form the polymeric lens body is freeof an organic diluent, or when the polymeric lens body is extracted inwater or an aqueous solution free of a volatile organic solvent, or whenthe polymeric lens body is free of a surface plasma treatment, or anycombination thereof.

One approach commonly used in the art to increase the wettability ofcontact lens surfaces is to apply treatments to the lens surfaces or tomodify the lens surfaces. In accordance with the present disclosure, thesilicone hydrogel contact lenses can have ophthalmically acceptablywettable lens surfaces without the presence of a surface treatment orsurface modification. Surface treatments include, for example, plasmaand corona treatments which increase the hydrophilicity of the lenssurface. While it is possible to apply one or more surface plasmatreatments to the present lens bodies, it is not necessary to do so inorder to obtain a silicone hydrogel contact lens having ophthalmicallyacceptably wettable lens surfaces when fully hydrated. In other words,in one example, the silicone hydrogel contact lenses of the presentdisclosure can be can be free of a surface plasma or corona treatment.

Surface modifications include binding wetting agents to the lenssurface, such as, for example, binding a wetting agent such as ahydrophilic polymer to at least a lens surface by chemical bonding oranother form of chemical interaction. In some cases, the wetting agentmay be bound to the lens surface as well as a least a portion of thepolymeric matrix of the lens, i.e., at least a portion of the bulk ofthe lens, by chemical bonding or another form of chemical interaction.The ophthalmically acceptably wettable lens surfaces of the presentdisclosure can be ophthalmically acceptably wettable without thepresence of a wetting agent (e.g., a polymeric material or anon-polymeric material) bound to at least the lens surface. While it ispossible to bind one or more wetting agents to the present lenses, it isnot necessary to do so in order to obtain a silicone hydrogel contactlens having ophthalmically acceptably wettable lens surfaces when fullyhydrated. Thus, in one example, the lenses of the present disclosure cancomprise wetting agents, such as, for example, hydrophilic polymers andincluding polyvinyl pyrrolidone, bound to a surface of the lens.Alternatively, in another example, the silicone hydrogel contact lensesof the present disclosure can be free of a wetting agent bound to thelens surface.

Another method of increasing lens wettability is to physically entrap awetting agent within the lens body or contact lens, such as byintroducing the wetting agent into the lens body when the lens body isswollen, and then returning the lens body to a less swollen state,thereby entrapping a portion of a wetting agent within the lens body.The wetting agent can be permanently trapped within the lens body, orcan be released from the lens over time, such as during wear. Theophthalmically acceptably wettable lens surfaces of the presentdisclosure can be ophthalmically acceptably wettable without thepresence of a wetting agent (e.g., a polymeric material or anon-polymeric material) physically entrapped in the lens body followingformation of the polymeric lens body. While it is possible to physicallyentrap one or more wetting agents in the present lenses, it is notnecessary to do so in order to obtain a silicone hydrogel contact lenshaving ophthalmically acceptably wettable lens surfaces when fullyhydrated. Thus, in one example, the lenses of the present disclosure cancomprise wetting agents, such as, for example, hydrophilic polymers andincluding polyvinyl pyrrolidone, entrapped within the lenses.Alternatively, the hydrogel contact lenses of the present disclosure,for example the silicone hydrogel contact lenses of the presentdisclosure, can be free of a wetting agent physically entrapped withinthe lens. As used herein, physically entrapped refers to immobilizing awetting agent, or other ingredient, in the polymeric matrix of the lenswith little or no chemical bonding or chemical interaction being presentbetween the wetting agent and or other ingredient and the polymericmatrix. This is in contrast to ingredients that are chemically bound tothe polymeric matrix, such as by ionic bonds, covalent bonds, van derWaals forces, and the like.

Another approach commonly used in the art to increase the wettabilityhydrogel contact lenses, for example silicone hydrogel contact lenses,includes adding one or more wetting agents to the polymerizablecomposition. In one example, the wetting agent can be a polymericwetting agent. However, the contact lenses of the present disclosure canhave ophthalmically acceptably wettable lens surfaces when thepolymerizable composition used to form the polymeric lens body is freeof a wetting agent. While it is possible to include one or more wettingagents in the present polymerizable compositions to increase thewettability of the hydrogel contact lenses of the present disclosure, itis not necessary to do so in order to obtain a hydrogel contact lenshaving ophthalmically acceptably wettable lens surfaces. In other words,in one example, the hydrogel contact lenses of the present disclosurecan be formed from polymerizable compositions free of wetting agents.Alternatively, in another example, the polymerizable compositions of thepresent invention can further comprise a wetting agent.

In one example, the wetting agent can be an internal wetting agent. Theinternal wetting agent can be bound within at least a portion of thepolymeric matrix of the lens. For example, the internal wetting agentcan be bound within at least a portion of the polymeric matrix of thelens by chemical bonding or another form of chemical interaction. Insome cases, the wetting agent may be bound to the lens surface as well.The internal wetting agent can comprise a polymeric material or anon-polymeric material. While it is possible to bind one or moreinternal wetting agents within the polymeric matrix of the presentlenses, it is not necessary to do so in order to obtain a hydrogelcontact lens having ophthalmically acceptably wettable lens surfaceswhen fully hydrated. Thus, in one example, the lenses of the presentdisclosure can comprise internal wetting agents bound to at least aportion of the polymeric matrix of the lens. Alternatively, in anotherexample, the hydrogel contact lenses of the present disclosure can befree of an internal wetting agent bound to at least a portion of thepolymeric matrix of the lens.

In another example, the wetting agent can be an internal polymericwetting agent. The internal polymeric wetting agent can be present inthe polymeric lens body as part of an interpenetrating polymer network(IPN) or a semi-IPN. An interpenetrating polymer network is formed by atleast two polymers, each of which is crosslinked to itself, but none ofwhich are crosslinked to each other. Similarly, a semi-IPN is formed byat least two polymers, at least one of which is crosslinked to itselfbut not to the other polymer, and the other of which is not crosslinkedeither to itself or the other polymer. In one example of the presentdisclosure, the contact lens can have ophthalmically acceptably wettablelens surfaces when the polymeric lens body is free of an internalpolymeric wetting agent present in the lens body as an IPN or asemi-IPN. Alternatively, the contact lens can comprise an internalpolymeric wetting agent present in the lens body as an IPN or asemi-IPN.

In yet another example, the wetting agent can be a linking compoundpresent in the polymerizable composition used to form the lens body, ora linking agent physically entrapped within the polymeric lens bodyafter the lens body has been formed. When the wetting agent is a linkingcompound, after polymerization of the lens body or entrapment of thelinking agent in the polymeric lens body, the linking compound cansubsequently link a second wetting agent to the lens body when the lensbody is contacted by the wetting agent. The linking can occur as part ofthe manufacturing process, for example as a washing process, or can takeplace when the lens body is contacted by a packaging solution. Thelinking can take the form of an ionic bond, or a covalent bond, or aform of van der Waals attraction. The linking agent can comprise aboronic acid moiety or group such that a polymerized boronic acid moietyor group is present in the polymeric lens body, or such that a boronicacid moiety or group is physically entrapped in the polymeric lens body.For example, when the linking agent comprises a form of boronic acid,the second wetting agent can comprise a form of poly(vinyl alcohol)which becomes bound to the form of boronic acid. Optionally, siliconehydrogel contact lenses of the present disclosure can be understood tobe free of linking agents. In one example, the silicone hydrogel contactlenses can be free of boronic acid moieties or groups, includingpolymerized boronic acid moieties or groups, that is, specifically, thesilicone hydrogel contact lenses can be formed from a polymerizablecomposition free of a form of boronic acid such as, for example, apolymerizable form of boronic acid including vinyl phenyl boronic acid(VPB), can be formed of a polymer free of units derived from apolymerizable form of boronic acid such as vinyl phenyl boronic acid(VPB), and the polymeric lens body and the silicone hydrogel contactlenses can be free of a form of boronic acid, including polymeric ornon-polymeric form of boronic acid, physically entrapped therein.Alternatively, the polymerizable composition, or the polymeric lensbody, or the hydrogel contact lens, or any combination thereof, cancomprise at least one linking agent.

In addition to including wetting agents in the polymerizable compositionand modifying the lens surfaces, washing polymeric lens bodies involatile organic solvents or aqueous solutions of volatile organicsolvent has been used to increase the wettability of lens surfaces,particularly silicone hydrogel contact lens surfaces. While it ispossible to wash the present polymeric lens bodies in a volatile organicsolvent or an aqueous solution of a volatile organic solvent, inaccordance with the present disclosure, it is not necessary to do so inorder to obtain a hydrogel contact lens having ophthalmically acceptablywettable lens surfaces when fully hydrated. In other words, in oneexample, the hydrogel contact lenses of the present invention have notbeen exposed to a volatile organic solvent, including a solution of avolatile organic solvent, as part of a manufacturing process. In oneexample, the hydrogel contact lenses of the present invention can beformed from a polymerizable composition free of a wetting agent, or thepolymeric lens body and/or hydrated contact lens can be free of awetting agent, or free of surface treatment, or free of a surfacemodification, or was not exposed to a volatile organic solvent duringthe manufacturing process, or any combination thereof. Instead, forexample, the hydrogel contact lenses can be washed in washing liquidfree of a volatile organic solvent, such as, for example, water or anaqueous solution free of a volatile organic solvent, including liquidsfree of a volatile lower alcohol.

The use of volatile organic solvents to extract lens bodies contributessignificantly to production costs, due to factors such as the cost ofthe organic solvents, the cost of disposal of the solvents, the need toemploy explosion-proof production equipment, the need to remove thesolvents from the lenses prior to packaging, and the like. However,development of polymerizable compositions capable of consistentlyproducing contact lenses with ophthalmically acceptably wettable lenssurfaces when extracted in aqueous liquid free of volatile organicsolvents can be challenging. For example, it is common to findnon-wetting regions present on the lens surfaces of contact lenses whichhave been extracted in aqueous liquid free of volatile organic solvents.

As previously discussed, in one example of the present disclosure, thecontact lenses are contact lenses which have not been exposed to avolatile organic solvent, such as a lower alcohol, during theirmanufacture. In other words, the washing, extraction and hydrationliquid used for such lenses, as well as all liquids used during wetdemolding, or wet delensing, or washing, or any other manufacturingstep, are all free of volatile organic solvents. In one example, thepolymerizable composition used to form these lenses which are notcontacted by a volatile organic solvent can comprise a hydrophilicvinyl-containing monomer or monomer component, such as, for example, ahydrophilic vinyl ether-containing monomer. The vinyl-containinghydrophilic monomer or monomer component can include, for example, VMA.The vinyl ether-containing monomers can include, for example, BVE, orEGVE, or DEGVE, or any combination thereof. In one particular example,the vinyl ether-containing monomer can be a vinyl ether-containingmonomer which is more hydrophilic than BVE, such as, for example, DEGVE.In another example, the hydrophilic monomer component of thepolymerizable composition can be a mixture of a first hydrophilicmonomer which is a vinyl-containing monomer but which is not a vinylether-containing monomer, and a second hydrophilic monomer which is avinyl ether-containing monomer. Such mixtures include, for example,mixtures of VMA and one or more vinyl ethers such as, for example, BVE,or DEGVE, or EGVE, or any combination thereof.

When present, the hydrophilic vinyl ether-containing monomer or monomercomponent can be present in the polymerizable composition in an amountfrom about 1 to about 15 unit parts, or from about 3 to about 10 unitparts. When present as a mixture with a hydrophilic vinyl-containingmonomer which is not a vinyl ether, the portion of the hydrophilicvinyl-containing monomer or monomer component which is not a vinyl etherand the hydrophilic vinyl ether-containing monomer or monomer componentcan be present in the polymerizable composition in a ratio of at least3:1, or from about 3:1 to about 15:1, or of about 4:1 based on the ratioof the unit parts by weight of the hydrophilic vinyl-containing monomeror monomer component which is not a vinyl ether to the unit parts byweight of the hydrophilic vinyl ether-containing monomer or monomercomponent.

Another approach for producing contact lenses having ophthalmicallyacceptably wettable lens surfaces in accordance with the presentdisclosure, particularly lenses extracted in a liquid free of a volatileorganic solvent and including lenses which are not contacted by avolatile organic solvent during manufacturing, can be to limit theamount of a vinyl-containing cross-linking agent or cross-linking agentcomponent included in the polymerizable composition. For example, avinyl-containing cross-linking agent or cross-linking agent componentcan be present in the polymerizable composition in an amount from about0.01 to about 0.80 unit parts, or from 0.01 to about 0.30 unit parts, orfrom about 0.05 to about 0.20 unit parts, or in an amount of about 0.1unit parts. In one example, a vinyl-containing cross-linking agent orcross-linking agent component can be present in the polymerizablecomposition in an amount effective to produce a contact lens havingimproved wettability as compared to a contact lens produced from thesame polymerizable composition but having an amount of thevinyl-containing cross-linking agent or cross-linking agent componentgreater than about 2.0 unit parts, or greater than 1.0 unit parts, orgreater than about 0.8 unit parts, or greater than about 0.5 unit parts,or greater than about 0.3 unit parts.

While limiting the amount of the vinyl-containing cross-linking agent orcross-linking agent component can improve wettability, in one example,the inclusion of a vinyl-containing cross-linking agent or cross-linkingagent component in the polymerizable composition can improve thedimensional stability of the resulting contact lens formed from thepolymerizable composition. Thus, in some polymerizable compositions, avinyl-containing cross-linking agent or cross-linking agent componentcan be present in the polymerizable in an amount effective to produce acontact lens having improved dimensional stability as compared to acontact lens produced from the same polymerizable composition butwithout the vinyl-containing cross-linking agent or cross-linking agentcomponent.

Yet another approach for producing contact lenses having ophthalmicallyacceptably wettable surfaces in accordance with the present disclosure,particularly lenses washed in a liquid free of a volatile organicsolvent, can be to include an amount of a vinyl-containing cross-linkingagent or cross-linking agent component in the polymerizable compositionbased on the ratio of the unit parts by weight of the hydrophilicvinyl-containing monomer or monomer component present in the compositionto the unit parts by weight of the vinyl-containing cross-linking agentor cross-linking agent component present in the composition. Forexample, the total unit parts of the hydrophilic vinyl-containingmonomer or monomer component and the total unit parts of thevinyl-containing cross-linking agent or cross-linking agent componentcan be present in the polymerizable composition in a ratio greater thanabout 125:1, or from about 150:1 to about 625:1, or from about 200:1 toabout 600:1, or from about 250:1 to about 500:1, or from about 450:1 toabout 500:1, based on the ratio of the unit parts by weight of all thehydrophilic vinyl-containing monomers present in the polymerizablecomposition to the total unit parts by weight of all thevinyl-containing cross-linking agents present in the polymerizablecomposition.

In one example, the contact lenses of the present disclosure areophthalmically compatible silicone hydrogel contact lenses. Manydifferent criteria can be evaluated to determine whether or not acontact lens is ophthalmically compatible, as will be discussed later.In one example, ophthalmically acceptable contact lenses haveophthalmically acceptably wettable surfaces when fully hydrated. Asilicone hydrogel contact lens having an ophthalmically acceptablywettable surfaces can be understood to refer to a silicone hydrogelcontact lens that does not adversely affect the tear film of a lenswearer's eye to a degree that results in the lens wearer experiencing orreporting discomfort associated with placing or wearing the siliconehydrogel contact lens on an eye.

An example of the disclosed polymerizable composition can be misciblewhen initially prepared, and can remain miscible over a period of timeadequate for the commercial manufacture of contact lenses, such as, forexample, for about 2 weeks, or about 1 week, or about 5 days. Typically,when polymerized and processed into contact lenses, misciblepolymerizable compositions result in contact lenses havingophthalmically acceptable clarifies.

Approaches commonly employed to increase the miscibility of hydrophilicmonomers and less hydrophilic or relatively hydrophobic monomers,including siloxane monomers, include adding organic diluents to thepolymerizable composition to act as compatiblizers between the morehydrophilic monomers and the less hydrophilic monomers. For example,siloxane monomers which typically are more hydrophobic. Also, when usingsiloxane monomers, using only siloxane monomers having low molecularweights (e.g., molecular weights below 2500 daltons) can also increasethe miscibility. In one example where the polymerizable compositioncomprises a first siloxane and a second siloxane monomer, the use of afirst siloxane of formula (6) as described above makes it possible toboth include both an optional high molecular weight second siloxane anda high level of the at least one hydrophilic monomer in thepolymerizable compositions of the present disclosure. And while it ispossible to include one or more organic diluents in the presentpolymerizable compositions disclosed herein, it may not be necessary todo so in order to obtain a miscible polymerizable composition inaccordance with the present disclosure. In other words, in one example,the hydrogel contact lenses of the present disclosure are formed frompolymerizable compositions which are free of an organic diluent.

The present hydrogel contact lenses may be provided in a sealed package.For example, the present hydrogel contact lenses may be provided insealed blister packs or other similar containers suitable for deliveryto lens wearers. The lenses may be stored in an aqueous solution, suchas a saline solution, within the package. Some suitable solutionsinclude phosphate buffered saline solutions and borate bufferedsolutions. The solutions may include a disinfecting agent if desired, ormay be free of a disinfecting or preservative agent. The solutions mayalso include a surfactant, such as a poloxamer and the like, if desired.

The lenses in the sealed packages are preferably sterile. For example,the lenses can be sterilized prior to sealing the package or can besterilized in the sealed package. The sterilized lenses may be lensesthat have been exposed to sterilizing amounts of radiation. For example,the lenses may be autoclaved lenses, gamma radiated lenses, ultravioletradiation exposed lenses, and the like.

With respect to the contact lens package, the package can furthercomprise a base member with a cavity configured to hold the contact lensbody and the packaging solution, and a seal attached to the base memberconfigured to maintain the contact lens and the packaging solution in asterile condition for a duration of time equivalent to a shelf life ofthe contact lens.

Certain specific examples of silicone hydrogel contact lenses will nowbe described, in accordance with the present teachings.

As one example (example A), a silicone hydrogel contact lens comprises apolymeric lens body that is the reaction product of a polymerizablecomposition comprising at least one hydrophilic monomer, at least onephosphine-containing compound, and at least one siloxane monomer. In oneexample, the at least one monomer comprises a first siloxane monomerrepresented by formula (6), wherein m of formula (6) represents oneinteger from 3 to 10, n of formula (6) represents one integer from 1 to10, R¹ is an alkyl group having from 1 to 4 carbon atoms, and each R² offormula (6) is independently either a hydrogen atom or a methyl group.

As a second example (example B), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A, and wherein thepolymerizable further comprises a second siloxane monomer. In oneexample, the first siloxane monomer and the second siloxane monomer canbe present in a ratio of at least 2:1 based on the unit parts by weightof the first siloxane monomer to the unit parts by weight of the secondsiloxane monomer present in the polymerizable composition.

As a third example (example C), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B, and whereinthe polymerizable composition further comprises a hydrophobic monomer ormonomer component. For example, the hydrophilic monomer can comprise orconsist of methyl methacrylate (MMA), or of EGMA, or any combinationthereof.

As a fourth example (example D), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C, andwherein the polymerizable composition further comprises avinyl-containing cross-linking agent or cross-linking agent component.In one example, the cross-linking agent or cross-linking agent componentcan comprise or consist of a vinyl ether-containing cross-linking agentor cross-linking agent component, specifically the cross-linking agentor cross-linking agent component can comprise or consist of triethyleneglycol divinyl ether (TEGVE).

As a fifth example (example E), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D, andwherein the polymerizable composition further comprises a thermalinitiator or thermal initiator component.

As a sixth example (example F), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or E,and wherein the at least one hydrophilic monomer comprises a hydrophilicmonomer component comprising a first hydrophilic monomer and a secondhydrophilic monomer. In one example, the first hydrophilic monomer cancomprise a hydrophilic amide-containing monomer, and the secondhydrophilic monomer can comprise a vinyl ether-containing monomer.

As a seventh example (example G), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F, and wherein the polymerizable composition further comprises a UVabsorbing agent or UV absorbing agent component.

As a eighth example (example H), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G, and wherein the polymerizable composition further comprises atinting agent or tinting agent component.

As an ninth example (example I), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G or H, and wherein the polymerizable composition comprises asiloxane monomer represented by formula (5), wherein R₁ of formula (5)is selected from either hydrogen atom or a methyl group; R₂ of formula(5) is selected from either of hydrogen or a hydrocarbon group having 1to 4 carbon atoms; m of formula (5) represents an integer of from 0 to10; n of formula (5) represents an integer of from 4 to 100; a and brepresent integers of 1 or more; a+b is equal to 20-500; b/(a+b) isequal to 0.01-0.22; and the configuration of siloxane units includes arandom configuration. As one example, the siloxane monomer can berepresented by formula (5), wherein m of formula (5) is 0, n of formula(5) is one integer from 5 to 10, a is one integer from 65 to 90, b isone integer from 1 to 10, R₁ of formula (5) is a methyl group, and R₂ offormula (5) is either a hydrogen atom or a hydrocarbon group having 1 to4 carbon atoms.

As a tenth example (example J), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G or H or I, and wherein the polymerizable composition furthercomprises a methacrylate-containing cross-linking agent or cross-linkingagent component, specifically the cross-linking agent or agent componentcan comprise or consist of ethylene glycol dimethacrylate (EGDMA). Inthis example, when the polymerizable composition also comprises a vinylether-containing cross-linking agent as part of the cross-linking agentcomponent, specifically the cross-linking agent component can compriseor consist of triethylene glycol divinyl ether (TGDVE) in combinationwith a methacrylate-containing cross-linking agent, which canspecifically comprise or consist of ethylene glycol dimethacrylate(EGDMA). In this example, it can be appreciated that the polymerizablecomposition comprises two cross-linking agents, each having differentreactivity ratios, i.e., the polymerizable composition comprises across-linking agent component comprising or consisting of avinyl-containing cross-linking agent and a methacrylate-containingcross-linking agent, the methacrylate-containing cross-linking agenthaving polymerizable functional groups which are more reactive and whichthus react at a faster rate than the vinyl polymerizable functionalgroups present in the vinyl-containing cross-linking agent.

As an eleventh example (example K), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G or H or I or J, and wherein the polymerizable compositionfurther comprises a chain transfer agent or chain transfer agentcomponent which can specifically comprise or consist of allyloxy ethanol(AE).

As a twelfth example (example L), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G or H or I or J or K, and wherein the at least one hydrophilicmonomer comprises a hydrophilic vinyl ether-containing monomer ormonomer component, for example, the hydrophilic vinyl ether-containingmonomer or monomer component can comprise or consist of 1,4-butanediolvinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethyleneglycol vinyl ether (DEGVE), or any combination thereof.

As a thirteenth example (example M), a silicone hydrogel contact lenscomprises a polymeric lens body that is the reaction product of apolymerizable composition as described in example A or B or C or D or Eor F or G or H or I or J or K or L, wherein the contact lens has theophthalmically acceptably wettable lens surfaces when the polymerizablecomposition used to form the lens is free of an internal wetting agent,or when the polymerizable composition used to form the polymeric lensbody is free of an organic diluent, or when the polymeric lens body isextracted in a liquid free of a volatile organic solvent, or when thelens is free of a surface plasma treatment, or any combination thereof.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the amount of the first siloxanemonomer can be from 20 to 45 unit parts of the polymerizablecomposition. The amount of the first siloxane monomer can be from 25 to40 unit parts of the polymerizable composition. The amount of the firstsiloxane monomer can be from 27 to 35 unit parts of the polymerizablecomposition.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the amount of the optional secondsiloxane monomer can be from 1 to 20 unit parts of the polymerizablecomposition. The amount of the second siloxane monomer can be from 2 to15 unit parts of the polymerizable composition. The amount of the secondsiloxane monomer can be from 5 to 13 unit parts of the polymerizablecomposition. In another example, the ratio of the unit parts of thefirst siloxane monomer to the second siloxane can be at least 1:1, or atleast 2:1.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the amount of the hydrophilic monomeror monomer component present in the polymerizable composition can befrom 1 to 60 unit parts of the polymerizable composition. Thehydrophilic monomer component can constitute from 4 to 60 unit parts ofthe polymerizable composition. When the hydrophilic monomer comprises orconsists of VMA, it can be present in an amount from 30 unit parts to 60unit parts. VMA can be present in the polymerizable composition in anamount from about 40 unit parts to about 50 unit parts. When thehydrophilic monomers, N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), or 2-hydroxylbutyl methacrylate (HOB), or anycombination thereof are present in the polymerizable composition as thehydrophilic monomer in the hydrophilic monomer component, each or allcan be present in amounts from about 3 to about 10 unit parts.

In any or each of the foregoing examples A-M as well as any or all otherexamples disclosed herein, the amount of the hydrophobic monomer ormonomer component present in the polymerizable composition can be from 1to 30 unit parts of the polymerizable composition. For example, thetotal amount of hydrophobic monomer or monomer component can be fromabout 5 to about 20 unit parts of the polymerizable composition. Inpolymerizable compositions in which the hydrophobic monomer MMA ispresent as the hydrophobic monomer or as part of the hydrophobic monomercomponent, the MMA can be present in an amount from about 5 to about 20unit parts, or from about 8 to about 15 unit parts.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the amount of the cross-linking agentor cross-linking agent component present in the polymerizablecomposition can be from 0.01 to 4 unit parts of the polymerizablecomposition. TEGDVE can be present in amounts from 0.01 to 1.0 unitparts. EGDMA can be present in amounts from 0.01 to 1.0 unit parts.TEGDMA can be present in amounts from 0.1 to 2.0 unit parts. Each ofthese non-silicon cross-linking agents can be present alone or in anycombination in the polymerizable composition.

In any or each of the foregoing examples A-M as well as any or all otherexamples disclosed herein, when the polymerizable composition containsEGMA, BVE, DEGVE, EGVE, or any combination thereof, they are eachpresent in amounts from 1 unit part to 20 unit parts of thepolymerizable composition. EGMA can be present in an amount from about 2unit parts to about 15 unit parts. BVE can be present in an amount from1 unit part to about 15 unit parts. BVE can be present in an amount fromabout 3 unit parts to about 7 unit parts. DEGVE can be present in anamount from 1 unit part to about 15 unit parts. DEGVE can be present inan amount from about 7 unit parts to about 10 unit parts. EGVE can bepresent in an amount from 1 unit part to about 15 unit parts, or in anamount from about 3 unit parts to about 7 unit parts.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the other optional components, such asinitiators or initiator component, tinting agents or tinting agentcomponents, UV absorbing agents or UV absorbing agent components, chaintransfer agents or chain transfer agent components, can each be presentin amounts from about 0.01 unit parts to about 3 unit parts. Aninitiator or initiator component can be present in the polymerizable inan amount from 0.1 unit parts to 1.0 unit parts. When a thermalinitiator or thermal initiator component is present, such as Vazo-64, itcan be present in an amount from about 0.3 to about 0.5 unit parts.Tinting agents or tinting agent components can be present in amountsfrom 0.01 unit parts to 1 unit part. When reactive dyes are used astinting agents or as part of a tinting agent component, such as ReactiveBlue 246 or Reactive Blue 247, they can each be present in amounts ofabout 0.01 unit parts. UV absorbing agents or UV absorbing agentcomponents can be present in amounts from 0.1 unit parts to 2.0 unitparts. For example, the UV absorbing agent UV1 described in the Examples1-37 below can be present in an amount from about 0.8 to about 1.0 unitparts, such as 0.9 unit parts; or the UV absorbing agent UV2 describedin the Examples 1-37 below, can be present in an amount from 0.5 unitparts to 2.5 unit parts, such as from about 0.9 unit parts to about 2.1unit parts. Oxygen scavengers or oxygen scavenger components can bepresent in amounts from 0.1 unit parts to 1.0 unit parts. As an example,when triphenyl phosphine (TPP) or diphenyl(P-vinylphenyl)phosphine(pTPP) or any combination thereof is used as the phosphine-containingcompound in the polymerizable composition, each or the combination canbe present in an amount from 0.3 unit parts to 0.7 unit parts, such asabout 0.5 unit parts. Chain transfer reagents or chain transfer reagentcomponents can be present in the polymerizable composition in an amountfrom 0.1 unit parts to 2.0 unit parts, and in many of Examples 1-37below is present in an amount from 0.2 unit parts to 1.6 unit parts. Forexample, the chain transfer reagent allyloxy ethanol (AE) can be presentin an amount from about 0.3 to about 1.4 unit parts.

In any or each of the foregoing examples A-M, as well as any or allother examples disclosed herein, the silicone hydrogel contact lensescan be free of a wetting agent that is present in the polymerizablecomposition, or in the polymeric lens body, or in the silicone hydrogelcontact lens. Similarly, the silicone hydrogel contact lens can havelens surfaces that are free of a surface treatment or a surfacemodification. However, in another example, the silicone hydrogel contactlens can include at least one wetting agent (i.e., a single wettingagent or two or more wetting agents present as a wetting agentcomponent) in the polymerizable composition, in the polymeric lens body,or in the silicone hydrogel contact lens. The silicone hydrogel contactlens can have treated or modified lens surfaces. In addition oralternatively, any or each of the foregoing examples A-M, as well as anyor all other examples of silicone hydrogel contact lenses disclosedherein, the contact lenses can be understood to be free of a linkingagent such as, for example, a form of boronic acid.

In another example, new polymerizable compositions are provided,including each and every polymerizable composition described herein inreference to the silicone hydrogel contact lenses and methods. Thepolymerizable compositions can be diluent-free in that they do notcontain an organic solvent, such as alcohols and the like, which canhelp reduce phase separation of the polymerizable composition. However,such diluent-free polymerizable compositions can still contain one ormore chain transfer agents, such as allyloxy ethanol. However, ifdesired, the polymerizable composition can include a diluent or adiluent component, which can be present in an amount from 1 to 20 unitparts.

As described herein, the present hydrogel contact lenses which comprisepolymeric lens bodies that comprise units derived from the at least onehydrophilic monomer, including silicone hydrogel contact lenses thatcomprise units derived from the at least one hydrophilic monomer and atleast one siloxane monomer; when fully hydrated, have an averageequilibrium water content (EWC) from about 30% wt/wt to about 70% wt/wt,or an average oxygen permeability of at least 55 barrers, or an averagecaptive bubble dynamic advancing contact angle less than 70 degrees, oran average captive bubble static contact angle less than 55 degrees, orany combination thereof, based on averages of values determined for atleast 20 individual lenses of the batch. Thus, the present disclosurealso relates to a batch of hydrogel contact lenses.

As used herein, a batch of hydrogel contact lenses refers to a group oftwo or more hydrogel contact lenses, and frequently, a batch refers toat least 10, or at least 100, or at least 1,000 hydrogel contact lenses.In accordance with the present disclosure, a batch of hydrogel contactlenses comprises a plurality of any of the hydrogel contact lensesdescribed herein, including the silicone hydrogel contact lensesdescribed herein.

In one example, the hydrogel contact lenses of the batch can have anaverage axial edge lift (AEL) variance based on averaging the AELmeasurements of a representative number of lenses from the batch atdifferent time points. For a batch of lenses, an average AEL variance ofless than plus or minus one hundred percent (±100%), or of less thanplus or minus fifty percent (±50%), or of less than twenty percent(±20%) over a time period from two weeks to seven years at roomtemperature or, when stored under accelerated shelf life testingconditions, for a period of time and temperature equivalent to storagefrom two weeks to seven years at room temperature, may be considered tobe acceptable. In one example, accelerated shelf life testing conditionswhich are especially useful in determining average AEL variance are for4 weeks at 70 degrees C., although other periods of time and temperaturecan be used. The average AEL variance is determined by averaging the AELvalues for each of the representative lenses using the actual AELmeasurements of the representative lenses before (AEL_(Initial)) andfollowing (AEL_(Final)) storage at room temperature or under acceleratedshelf life conditions. The average AEL variability is determined usingthe following equation (A):

((AEL_(Final)−AEL_(Initial))/AEL_(Initial))×100  (A).

On average, the AELs of the hydrogel contact lenses of the batch vary byless than twenty percent in either direction of a target value, or lessthan ten percent in either direction of a target value, or less thanfive percent in either direction of a target value. As one example, if acontact lens has a target AEL of 20 μm±50%, the present batch ofhydrogel contact lenses will have an average AEL from 10 μm to 30 μmover the course of the shelf life study. A representative number oflenses tested from the batch can be 20 or more individual lenses.

In accelerated shelf life studies, the lens properties such as AEL orcolor value can be determined for contact lenses that were stored for aperiod of time at an elevated temperature, such as above 40 degrees C.,such as 50 degrees C., or 55 degrees C., or 65 degrees C., or 70 degreesC., or 80 degrees C., or 95 degrees C., and the like. Or, the lensproperties can be determined for contact lenses that were stored for aperiod of time at room temperature (e.g., about 20-25 degrees C.).

For accelerated shelf life studies, the following formula can be used todetermine the number of months of storage at a particular temperaturethat are equivalent to storage of the desired length of time at roomtemperature:

Desired shelf life=[N×2y]+n  (B)

where

N=number of months of storage under accelerated conditions

2y=acceleration factor

y=2.0 for each 10° C. above room temperature (25° C.), for storage at orabove 45° C.

y=1.0 for each 10° C. above room temperature (25° C.), for storage from35° C. to 45° C.

n=age of lenses (in months) at start of the study

Based on this equation, the following storage times have beencalculated: 6 months of storage at 35 degrees C. is equivalent to 1 yearaging at 25 degrees C., 3 months of storage at 45 degrees C. isequivalent to 1 year of aging at 25 degrees C., 3 months of storage at55 degrees C. is equivalent to 2 years of aging at 25 degrees C., and 3months of storage at 65 degrees C. is equivalent to 4 years of aging at25 degrees C.

In one example, the batch comprises a batch of hydrogel contact lensescomprising a plurality of the hydrogel contact lenses in accordance withthe present disclosure, wherein the batch of hydrogel contact lenses hasat least two average values selected from an average oxygen permeabilityof at least 55 barrers, an average tensile modulus from about 0.2 MPa toabout 0.9 MPa when fully hydrated, and an average EWC from about 30%wt/wt to about 70% wt/wt; based on averages of values determined for atleast 20 individual lenses of the batch.

In one example, when initially tested shortly after manufacturing andthen tested again at a later time point, a batch of lenses can exhibit achange in its average physical dimensions. As batches of lenses inaccordance with the present disclosure are dimensionally stable, theycan exhibit an acceptable level of change in their average physicaldimensions. As used herein, dimensional stability variance is understoodto refer to a variance in a value of a physical dimension between avalue of the physical dimension determined when the batch of lenses isinitially tested shortly after its manufacture, and the value of thephysical dimension determined when the batch of lenses is tested againat a later time point. The later time point can be, for example, from atleast 2 weeks after the initial time point, to up to 7 years after theinitial time point. The silicone hydrogel contact lenses of the batchhave an average dimensional stability variance of less than plus orminus three percent (±3.0%) based on averaging the lens diametermeasurements of a representative number of lenses from the batch, suchas, for example, 20 lenses from the batch. For a batch of lenses, anaverage dimensional stability variance of less than plus or minus threepercent (±3.0%), where the average dimensional stability variance is thevariance in a value of a physical dimension when measured at an initialtime point within one day of a manufacturing date of the batch oflenses, and at a second time point, where the second time point is fromtwo weeks to seven years after the initial time point when the batch isstored at room temperature, or, when the batch is stored at a highertemperature (i.e., under accelerated shelf life testing conditions), thesecond time point is a time point representative of storage of the batchfrom two weeks to seven years at room temperature, is considered to be adimensionally stable batch. In one example, accelerated shelf lifetesting conditions which are especially useful in determining averagedimensional stability variance are for 4 weeks at 70 degrees C.,although other periods of time and other temperatures can be used. Theaverage dimensional stability variance is determined by averaging theindividual dimensional stability variances for each of therepresentative lenses using the actual diameters of representativelenses measured initially (Diameter_(original)) and the actual diametersof representative lenses measured following (Diameter_(Final)) storageat room temperature or under accelerated shelf life conditions. Therepresentative lenses measured initially and the representative lensesmeasured following storage can be the same lenses or can be differentlenses. As used herein, the average dimensional stability variance isrepresented as a percent (%). The individual dimensional stabilityvariances are determined using the following equation (C):

((Diameter_(Final)−Diameter_(original))/Diameter_(Original))×100  (C).

On average, the diameters of the silicone hydrogel contact lenses of thebatch vary by less than three percent in either direction of a targetvalue (±3.0%). As one example, if a contact lens has a target diameter(chord diameter) of 14.20 mm, the present batch of hydrogel contactlenses will have an average diameter (average of the population in thebatch) from 13.77 mm to 14.63 mm. In one example, the dimensionalstability variance is less than plus or minus two percent (±2.0%). Asone example, if a contact lens has a target diameter (chord diameter) of14.20 mm, the present batch of hydrogel contact lenses will have anaverage diameter (average of the population in the batch) from 13.92 mmto 14.48 mm. Preferably, the average diameter of the batch of hydrogelcontact lenses does not vary by more than plus or minus 0.20 mm from thetarget diameter, which is commonly from 13.00 mm to 15.00 mm.

In accelerated shelf life studies, the average dimensional stabilityvariance can be determined for contact lenses that were stored for aperiod of time at an elevated temperature, such as above 40 degrees C.,including, for example, 50 degrees C., or 55 degrees C., or 65 degreesC., or 70 degrees C., or 80 degrees C., or 95 degrees C., and the like.Or, the average dimensional stability can be determined for contactlenses that were stored for a period of time at room temperature (e.g.,about 20-25 degrees C.).

Another example of the present disclosure provides methods ofmanufacturing hydrogel contact lenses. In accordance with the presentteachings, the method comprises providing a polymerizable composition.

The method can also comprise a step of polymerizing the polymerizablecomposition to form a polymeric lens body. The step of polymerizing thepolymerizable composition can be conducted in a contact lens moldassembly. The polymerizable composition can be cast molded between moldsformed of a thermoplastic polymer. The thermoplastic polymer used toform the molding surfaces of the mold can comprise a polar polymer, orcan comprise a non-polar polymer. Alternatively, the polymerizablecomposition can be formed into a lens via various methods known to thoseof ordinary skill in the art, such as spin casting, injection molding,forming a polymerized rod that is subsequently lathed to form a lensbody, etc.

The polymerization of the polymerizable composition can be initiatedthermally or using light, such as using ultra-violet (UV) light. In someexamples, the polymerization can be conducted in an atmospherecomprising air, or in an inert atmosphere.

The method can also comprise contacting the polymeric lens body with awashing liquid to remove extractable material, such as unreactedmonomers, uncross-linked materials that are otherwise not physicallyimmobilized in the polymeric lens body, diluents, and the like. Thewashing liquid can be a liquid free of a volatile organic solvent, orcan comprise a volatile organic solvent (e.g., can be a volatile organicsolvent or a solution of a volatile organic solvent).

The contacting can be effective to remove at least a portion ofphosphine-containing or phosphine oxide-containing components from thepolymeric lens body. As previously discussed, the washing liquid can bewater or an aqueous solution free of a volatile organic solvent, or canbe an organic solvent or a solution of an organic solvent.Alternatively, in some examples, the method does not comprise a step ofcontacting the polymeric lens body with a washing liquid or any liquid,i.e., where the polymeric lens body is not contacted with any liquidprior to being placed into a blister package with packaging solution andsealed. The method can be a method not comprising a washing stepinvolving the use of a washing liquid comprising a volatile organicsolvent, i.e., where the polymeric lens body is contacted by a washingliquid, but is not contacted with a washing liquid comprising a volatileorganic solvent, and is not contacted by a volatile organic solventprior to being placed into a blister package with packaging solution andsealed.

In methods including a step of contacting the lens body with a washingliquid, the step of contacting the polymeric lens body with a washingliquid can be understood to be an extraction step because extractablematerials are removed from the polymeric lens body. In some methods, thecontacting step comprises contacting the polymeric lens body with awashing liquid comprising a volatile organic solvent, such as a liquidcontaining a primary alcohol, such as methanol, ethanol, n-propylalcohol, and the like. Some washing liquid may contain a secondaryalcohol, such as isopropyl alcohol, and the like. Using a washing liquidcontaining one or more volatile organic solvents can be helpful inremoving hydrophobic materials from the polymeric lens body, and thusmay increase the wettability of the lens surfaces. Such methods may beunderstood to be alcohol-based extraction steps. In other methods, thecontacting step comprises contacting the polymeric lens body with anaqueous washing liquid that is free of a volatile organic solvent. Suchmethods may be understood to be aqueous extractions steps. Examples ofaqueous washing liquid that can be used in such methods include water,such as deionized water, saline solutions, buffered solutions, oraqueous solutions containing surfactants or other non-volatileingredients that may improve the removal of hydrophobic components fromthe polymeric contact lens bodies, or may reduce distortion of thepolymeric contact lens bodies, compared to the use of deionized wateralone. In one example, when washed using a washing liquid free ofvolatile organic solvents, the surfaces of the lens bodies of thepresent disclosure have ophthalmically acceptable wettable surfaces.

In some examples, the polymeric lens body can be exposed to an oxidizingstep to oxidize the phosphine-containing compound present in thepolymeric lens body. The oxidizing step can be effective to oxidize themajority of the phosphine-containing compound present in the polymericlens body, or to oxidize the majority of the phosphine-containingcompound present on the surface of the lens body. The oxidizing step cancomprise exposing the polymeric lens body to hydrogen peroxide, such as,for example, hydrogen peroxide gas or an aqueous solution of hydrogenperoxide or a solution of hydrogel peroxide free of a lower alcohol. Forsome phosphine-containing compounds, such as, for example, TPP, theoxidized form (the phosphine oxide) has greater aqueous solubility thanthe non-oxidized form. For formulations containing these forms ofphosphine-containing compounds, it can be helpful to expose thepolymeric lens bodies to an oxidizing agent prior to exposing the lensbodies to a washing step, in order to increase the amount ofphosphine-containing compound extracted from the lens bodies (byextracting the phosphine-containing compound in its oxide form).

After washing, the contact lenses can be placed in packages, such asplastic blister packs, with a packaging solution, such as a bufferedsaline solution, which may or may not contain surfactants,anti-inflammatory agents, anti-microbial agents, contact lens wettingagents, and the like, and are sealed and sterilized. The packagingsolution used to package the silicone hydrogel contact lenses of thepresent disclosure can comprise a wetting agent to increase wettabilityof the lens surfaces. However, it will be understood that the lenssurfaces of the silicone hydrogel contact lenses of the presentdisclosure have ophthalmically acceptable wettable surfaces prior tocontact with a packaging solution comprising a wetting agent, and theuse of a wetting agent in the packaging solution is only to increase thewettability of the already ophthalmically acceptable wettable surfaces,and thus is not needed to provide the contact lens with anophthalmically acceptable wettable surface.

After washing, the contact lenses can be placed in packages, such asplastic blister packs, with a packaging solution, such as a bufferedsaline solution, which may or may not contain surfactants,anti-inflammatory agents, anti-microbial agents, contact lens wettingagents, and the like, and can be sealed and sterilized.

In accordance with the present disclosure, the polymeric lens body canbe packaged along with a contact lens packaging solution in a contactlens package, such as a blister pack or glass vial. Following packaging,the package can be sealed and the polymeric lens body and the contactlens packaging solution can be sterilized, for example, by autoclavingthe sealed package, to produce a silicone hydrogel contact lens product.

The present method can further comprise repeating the steps to produce aplurality of the hydrogel contact lenses. The present method can furthercomprise manufacturing a batch of hydrogel contact lenses.

EXAMPLES

The following Examples 1-37 illustrate certain aspects and advantages ofthe present invention, which should be understood not to be limitedthereby.

The following chemicals are referred to in Examples 1-37, and may bereferred to by their abbreviations.

Si1: 2-propenoic acid, 2-methyl-,2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1-yl)propoxy]ethylester (CAS number of 1052075-57-6). (Si1 was obtained from Shin-EtsuChemical Co., Ltd. (Japan) as product number X-22-1622).

Si2: α,ω-Bis(methacryloxypropyl)-poly(dimethylsiloxane)-poly(ω-methoxy-poly(ethylenegylcol)propylmethylsiloxane) (thesynthesis of this compound can be performed as described inUS20090234089)

Si3: Poly(dimethyl siloxane), methacryloxypropyl terminated (CAS number58130-03-3; DMS-R18 available from Gelest, Morrisville, Pa.)

Si4: SiGMA:3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane(available from Gelest, Morrisville, Pa.)

Si5: TRIS: 3-[Tris(trimethylsilyloxy)silyl]propyl methacrylate

Si6: MCS-M11: A monomethacryloxypropyl terminated polydimethylsiloxane(Gelest, Morrisville, Pa., USA).

VMA: N-vinyl-N-methylacetamide (CAS number 003195786)

DMA: N,N-dimethylacrylamide (CAS number 2680-03-7)

HEMA: 2-hydroxyethyl methacrylate (CAS number 868-77-9)

HOB: 2-hydroxylbutyl methacrylate (CAS number 29008-35-3)

EGMA: Ethylene glycol methyl ether methacrylate (CAS number 6976-93-8)

MMA: Methyl methacrylate (CAS number 80-62-6)

EGDMA: Ethylene glycol dimethacrylate (CAS number 97-90-5)

TEGDMA: triethylene glycol dimethacrylate (CAS number 109-16-0)

BVE: 1,4-butanediol vinyl ether (CAS number 17832-28-9)

DEGVE: diethylene glycol vinyl ether (CAS number 929-37-3)

EGVE: ethylene glycol vinyl ether (CAS number 764-48-7)

TEGDVE: triethylene glycol divinyl ether (CAS number 765-12-8)

AE: 2-Allyloxy ethanol (CAS number 111-45-5)

V-64: 2,2′-Azobis-2-methyl propanenitrile (CAS number 78-67-1)

UV1: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (CAS number16432-81-8)

UV2: 2-(3-(2H-benzotriazol-2-YL)-4-hydroxy-phenyl)ethyl methacrylate(CAS number 96478-09-0)

RBT1: 1,4-Bis[4-(2-methacryloxyethyl)phenylamino]anthroquinone (CASnumber 121888-69-5)

RBT2: 1,4-Bis[(2-hydroxyethyl)amino]-9,10-anthracenedionebis(2-propenoic)ester (CAS Reg. No. 109561071)

TPP: Triphenyl phosphine (CAS number 603-35-0)

pTPP: polymerizable TPP: diphenyl(P-vinylphenyl)phosphine (CAS number40538-11-2)

Hydrogel Contact Lens Fabrication and Testing Procedure

The chemical compounds set forth in Examples 1-37 were, for eachexample, weighed out in amounts corresponding to the described unitparts, and combined to form a mixture. The mixture was filtered througha 0.2-5.0 micron syringe filter into a bottle. Mixtures were stored forup to about 2 weeks. The mixtures are understood to be polymerizablesilicone hydrogel contact lens precursor compositions, or as usedherein, polymerizable compositions. In Examples 1-37, the listed amountsof ingredients are given as unit parts of the polymerizable compositionby weight.

A volume of the polymerizable composition was cast molded by placing thecomposition in contact with a lens defining surface of a female moldmember. In all of the following Examples 1-37, the molding surface ofthe female mold member was formed of a non-polar resin, specificallypolypropylene. A male mold member was placed in contact with the femalemold member to form a contact lens mold assembly comprising a contactlens shaped cavity containing the polymerizable composition. In thefollowing Examples 1-37, the molding surface of the male mold member wasformed of a non-polar resin, specifically polypropylene.

Contact lens mold assemblies were placed in a nitrogen flushed oven toallow the precursor compositions to thermally cure. For all of Examples1-37, the contact lens mold assemblies were exposed to temperatures ofat least about 55° C. for about 2 hours. Examples of curing profileswhich can be used to cure silicone hydrogel contact lenses describedherein include exposing the contact lens mold assemblies to temperaturesof 55° C. for 40 minutes, 80° C. for 40 minutes, and 100° C. for 40minutes. Other contact lenses can be made with the same curing profile,but instead of the first temperature being at 55° C., it can be at 65°C.

After polymerizing the polymerizable compositions, the contact lens moldassemblies were demolded to separate the male and female mold members.The polymeric lens body remained adhered to the male mold or the femalemold. A dry demolding process where the mold assembly is not contactedwith a liquid medium can be used, or a wet demolding process where themold assembly is contacted with a liquid medium such as, for example,water or an aqueous solution, can be used. A mechanical dry demoldingprocess can involve applying mechanical force to a portion of one orboth of the mold members in order to separate the mold members. In allof the following Examples 1-37, a dry demolding process was used.

The polymeric lens body was then delensed from the male mold or femalemold to produce a delensed polymeric lens body. In one example of adelensing method, the polymeric lens body can be delensed from the malemold member using a dry delensing process, such as by manually peelingthe lens from the male mold member or by compressing the male moldmember and directing a gas toward the male mold member and the polymericlens body, and lifting the dry polymeric lens body with a vacuum devicefrom the male mold member, which is discarded. In other methods, thepolymeric lens body can be delensed using a wet delensing process bycontacting the dry polymeric lens body with a liquid releasing medium,such as water or an aqueous solution. For example, a male mold memberwith the attached polymeric lens body can be dipped into a receptaclecontaining a liquid until the polymeric lens body separates from themale mold member. Or, a volume of liquid releasing medium can be addedto the female mold to soak the polymeric lens body in the liquid and toseparate the lens body from the female mold member. In the followingExamples 1-37, a dry delensing process was used. Following separation,the lens body can be lifted from the mold member manually using tweezersor using a vacuum device and placed into a tray.

The delensed lens product was then washed to remove extractablematerials from the polymeric lens body, and hydrated. Extractablematerials included polymerizable components such as, for example,monomers, or cross-linking agents, or any optional polymerizableingredients such as tints or UV blockers, or combinations thereof,present in the polymerizable composition which remain present in thepolymeric lens body in an unreacted form, in a partially reacted form,or in an uncross-linked form, or any combination thereof, followingpolymerization of the lens body and prior to extraction of the lensbody. Extractable materials may have also included any non-polymerizableingredients present in the polymerizable composition, for example, anyoptional non-polymerizable tinting agents, or UV blockers, or diluents,or chain transfer agent, or any combination thereof, remaining presentin the polymeric lens body following polymerization of the polymericlens body but prior to extraction of the polymeric lens body.

In another method, such as a method involving delensing by compressionof the male mold member and directing gas flow toward the male moldmember, the delensed polymerized contact lens bodies can be placed incavities of lens carriers or trays where the delensed polymeric lensbodies can then be contacted with one or more volumes of an extractionliquid, such as an aqueous extraction liquid free of a volatile organicsolvent, for example deionized water or an aqueous solution of asurfactant such as Tween 80, or an organic solvent-based extractionliquid such as ethanol, or an aqueous solution of a volatile organicsolvent such as ethanol.

In other methods, such as those involving wet delensing by contactingthe mold and lens with a liquid releasing medium, the delensedpolymerized contact lens bodies can be washed to remove extractablecomponents from the lens bodies using a washing liquid that is free of avolatile organic solvent, such as a lower alcohol, for example,methanol, ethanol, or any combination thereof. For example, the delensedpolymerized contact lens bodies can be washed to remove extractablecomponents from the lens bodies by contacting the lens bodies withaqueous washing liquid free of a volatile organic solvent, such as, forexample, deionized water, or a surfactant solution, or a salinesolution, or a buffer solution, or any combination thereof. The washingcan take place in the final contact lens package, or can take place a inwashing tray or a washing tank.

In the following Examples 1-37, following the dry demolding and drydelensing steps, the dry delensed lens bodies were placed in cavities oftrays, and the delensed polymeric lens bodies were extracted andhydrated by contacting the polymeric lens bodies with one or morevolumes of extraction liquid. The extraction and hydration liquid usedin the extraction and hydration process consisted of either a) acombination of volatile organic solvent-based extraction liquid andvolatile organic solvent-free hydration liquid, or b) volatile organicsolvent-free extraction and hydration liquid, i.e., entirelyaqueous-based extraction and hydration liquid. Specifically, in Examples1-5 below, the extraction and hydration process comprised at least twoextraction steps in separate portions of ethanol, followed by at leastone extraction step in a portion of a 50:50 wt/wt ethanol:water solutionof Tween 80, followed by at least three extraction and hydration stepsin separate portions of a solution of Tween 80 in deionized water,wherein each extraction or extraction and hydration step lasted fromabout 5 minutes to 3 hours. In Examples 6-25 below, the extraction andhydration process used comprised at least three extraction and hydrationsteps in separate portions of a solution of Tween 80 in deionized water,wherein the temperature of the Tween 80 solution of the portions rangedfrom room temperature to about 90 degrees C., and wherein eachextraction and hydration step lasted from about 15 minutes to about 3hours.

Washed, extracted and hydrated lenses were then placed individually incontact lens blister packages with a phosphate buffered saline packagingsolution. The blister packages were sealed and sterilized byautoclaving.

Following sterilization, lens properties such as contact angle,including dynamic and static contact angle, oxygen permeability,ionoflux, modulus, elongation, tensile strength, water content, and thelike were determined, as described herein.

For the present contact lenses, contact angles including dynamic andstatic contact angles, can be determined using routine methods known topersons of ordinary skill in the art. For example, the advancing contactangle and receding contact angle of the contact lenses provided hereincan be measured using a conventional drop shape method, such as thesessile drop method or captive bubble method.

In the following Examples 1-37, the advancing and receding contact angleof silicone hydrogel contact lenses was determined using a Kruss DSA 100instrument (Kruss GmbH, Hamburg), and as described in D. A. Brandreth:“Dynamic contact angles and contact angle hysteresis”, Journal ofColloid and Interface Science, vol. 62, 1977, pp. 205-212 and R.Knapikowski, M. Kudra: Kontaktwinkelmessungen nach demWilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung”, Chem.Technik, vol. 45, 1993, pp. 179-185, and U.S. Pat. No. 6,436,481, all ofwhich are incorporated by reference herein.

As an example, the advancing contact angle and receding contact anglewas be determined using a captive bubble method using phosphate bufferedsaline (PBS; pH=7.2). The lens was flattened onto a quartz surface andrehydrated with PBS for at least 10 minutes before testing. An airbubble was placed onto a lens surface using an automated syringe system.The size of the air bubble was increased and decreased to obtain thereceding angle (the plateau obtained when increasing the bubble size)and the advancing angle (the plateau obtained when decreasing the bubblesize).

The modulus, elongation, and tensile strength values of the presentlenses can be determined using routine methods known to persons ofordinary skill in the art, such as, for example, a test method inaccordance with ANSI Z80.20. The modulus, elongation, and tensilestrength values reported herein were determined by using an InstronModel 3342 or 3343 mechanical testing system (Instron Corporation,Norwood, Mass., USA) and Bluehill Materials Testing Software, using acustom built rectangular contact lens cutting die to prepare therectangular sample strip. The modulus, elongation and tensile strengthwere determined inside a chamber having a relative humidity of least70%. The lens to be tested was soaked in phosphate buffered solution(PBS) for at least 10 minutes prior to testing. While holding the lensconcave side up, a central strip of the lens was cut using the cuttingdie. The thickness of the strip was determined using a calibrated gauge(Rehder electronic thickness gauge, Rehder Development Company, CastroValley, Calif., USA). Using tweezers, the strip was loaded into thegrips of the calibrated Instron apparatus, with the strip fitting overat least 75% of the grip surface of each grip. A test method designed todetermine the maximum load (N), the tensile strength (MPa), the strainat maximum load (% elongation) and the mean and standard deviation ofthe tensile modulus (MPa) was run, and the results were recorded.

The percent energy loss of the present silicone hydrogel contact lensescan be determined using routine methods known to persons of ordinaryskill in the art. For the following Examples 1-37, the percent energyloss was determined using an Instron Model 3343 (Instron Corporation,Norwood, Mass., USA) mechanical testing system, with a 10N forcetransducer (Instron model no. 2519-101) and Bluehill Materials TestingSoftware including a TestProfiler module. The energy loss was determinedinside a chamber having a relative humidity of least 70%. Beforetesting, each lens was soaked in phosphate buffered solution (PBS) forat least 10 minutes. Using tweezers, the lens was loaded into the gripsof the calibrated Instron apparatus, with the lens loaded verticallybetween the grips as symmetrically as possible so that the lens fit overat least 75% of the grip surface of each grip. A test designed todetermine the energy required to stretch the lens to 100% strain andthen return it to 0% strain at a rate of 50 mm/minute was then run onthe lens. The test was conducted only once on a single lens. Once thetest was finished, energy loss was calculated using the followingequation: Lost Energy (%)=(Energy to 100% strain−Energy to return to 0%strain)/Energy to 100% strain×100%.

The ionoflux of the present lenses can be determined using routinemethods known to persons of ordinary skill in the art. For the lenses ofthe following Examples 1-37, the ionoflux was measured using a techniquesubstantially similar to the “Ionoflux Technique” described in U.S. Pat.No. 5,849,811, which is incorporated by reference herein. Prior tomeasurement, a hydrated lens was equilibrated in deionized water for atleast 10 minutes. The lens to be measured was placed in a lens-retainingdevice, between male and female portions. The male and female portionsincluded flexible sealing rings which were positioned between the lensand the respective male or female portion. After positioning the lens inthe lens-retaining device, the lens-retaining device was then placed ina threaded lid. The lid was screwed onto a glass tube to define a donorchamber. The donor chamber was filled with 16 ml of 0.1 molar NaClsolution. A receiving chamber was filled with 80 ml of deionized water.Leads of the conductivity meter were immersed in the deionized water ofthe receiving chamber and a stir bar was added to the receiving chamber.The receiving chamber was placed in a water bath and the temperature washeld at about 35° C. Finally, the donor chamber was immersed in thereceiving chamber such that the NaCl solution inside the donor chamberwas level with the water inside the receiving chamber. Once thetemperature inside the receiving chamber was equilibrated to 35 degreesC., measurements of conductivity were taken every 2 minutes for at least10 minutes. The conductivity versus time data was substantially linear,and was used to calculate the ionoflux value for the lenses tested.

The oxygen permeability (Dk) of the present lenses can be determinedusing routine methods known to persons of ordinary skill in the art. Forexample, the Dk value can be determined using a commercially availableinstrument under the model designation of MOCON® Ox-Tran System (MoconInc., Minneapolis, Minn., USA), for example, using the Mocon Method, asdescribed in U.S. Pat. No. 5,817,924, which is incorporated by referenceherein. The Dk values of the lenses of the following Examples 1-37 weredetermined using the method described by Chhabra et al. (2007), Asingle-lens polarographic measurement of oxygen permeability (Dk) forhypertransmissible soft contact lenses. Biomaterials 28: 4331-4342,which is incorporated by reference herein.

The equilibrium water content (EWC) of the present lenses can bedetermined using routine methods known to persons of ordinary skill inthe art. For the lenses of the following Examples 1-37a hydratedsilicone hydrogel contact lens was removed from an aqueous liquid, wipedto remove excess surface water, and weighed. The weighed lens was thendried in an oven at 80 degrees C. under a vacuum, and the dried lens wasthen weighed. The weight difference was determined by subtracting theweight of the dry lens from the weight of the hydrated lens. The watercontent (%) is the (weight difference/hydrated weight)×100.

The percentage of the wet extractable component or dry extractablecomponent in a lens can be determined by extracting the lenses in anorganic solvent in which the polymeric lens body is not soluble inaccordance to methods known to those of ordinary skill in the art. Forthe lenses of the following Examples 1-37, an extraction in methanolusing a Sohxlet extraction process was used. For determination of thewet extractable component, a sample (e.g., at least 5 lenses per lot) offully hydrated and sterilized contact lenses was prepared by removingexcess packaging solution from each lens and drying them overnight in an80° C. vacuum oven. For determination of the dry extractable component,a sample of polymeric lens bodies which had not been washed, extracted,hydrated or sterilized was prepared by drying the lens bodies overnightin an 80° C. vacuum oven. When dried and cooled, each lens was weighedto determine its initial dry weight (W1). Each lens was then placed in aperforated, stackable Teflon thimble, and the thimbles were stacked toform an extraction column with an empty thimble placed at the top of thecolumn. The extraction column was placed into a small Sohxlet extractorattached to a condenser and a round bottom flask containing 70-80 mlmethanol. Water was circulated through the condenser and the methanolwas heated until it gently boiled. The lenses were extracted for atleast 4 hours from the time condensed methanol first appeared. Theextracted lenses were again dried overnight at 80° C. in a vacuum oven.When dried and cooled, each lens was weighed to obtain the dry weight ofthe extracted lens (W2), and the following calculation was made for eachlens to determine the percent wet extractable component:[(W1-W2)/W1]×100.

Examples 1-28

Table 1 lists the ingredients of polymerizable compositions 1-14. Table2 lists the ingredients of polymerizable compositions 15-28.Polymerizable compositions 1-28 were prepared as described in theHydrogel Contact Lens Fabrication and Testing Procedure given above, andwere used to prepare and test hydrogel contact lenses as described inthe Hydrogel Contact Lens Fabrication and Testing Procedure. All of thelenses prepared in Examples 1-28 were manually dry demolded anddelensed. With the exception of polymerizable composition 1, all of thepolymerizable compositions include a phosphine-containing component(either TPP or pTPP).

Table 3 shows the lens properties for lenses formed using polymerizablecompositions 1-14 when initially manufactured. Table 4 shows the lensproperties for lenses formed using polymerizable compositions 15-28 wheninitially manufactured. Hydrogel contact lenses formed frompolymerizable compositions 2-28 had acceptable lens properties wheninitially manufactured, as shown in Tables 3 and 4.

The hydrogel contact lenses formed from polymerizable compositions 2-28also had acceptable shape retention and color value both when initiallymanufactured and after storage for at least 1 month at room temperature,and at least 2 weeks at elevated temperatures. For example, lenses offormulations 2, 3, and 4 had acceptable shape retention after beingstored for at least 20 days at 95 degrees C. Lenses of formulations 5,6, 7, 8, 11, 12, 14, 15, 16, 18, 19, 20, 24 and 25 had acceptable shaperetention after being stored for at least 14 days at 80 degrees C.Lenses of formulation 9 had acceptable shape retention after beingstored for at least 6 days at 95 degrees C. Lenses of formulation 10 and13 had acceptable shape retention after being stored for at least 7 daysat 80 degrees C. Lenses of formulation 17, 21, 22, and 23 had acceptableshape retention after being stored for at least 4.4 weeks at 80 degreesC.

TABLE 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Si1 30 30 30 30 30 32 32 23 2326 26 26 26 26 Si2 10 10 15 15 10 10 10 10 10 Si3 3 3 3 4 4 2 2 VMA 4545 45 45 48 40 50 40 45 40 45 45 40 45 DMA HEMA HOB BVE 7 7 7 7 5 5 7 5DEGVE EGVE MMA 15 15 15 15 15 12 14 10 10 12 12 12 12 12 EGMA 7 7 7 7 75 5 5 2 5 TEGDVE 0.10 0.10 0.10 0.10 0.30 0.20 0.10 0.10 0.10 0.20 0.200.20 0.20 EGDMA 0.50 0.50 0.50 0.50 TEGDMA 0.80 1.00 0.80 1.00 1.00 1.201.20 1.20 1.30 1.10 AE 0.5 0.8 1.4 1.4 1.4 V64 0.30 0.30 0.50 0.50 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 UV2 0.90 0.90 0.90 0.900.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 UV1 0.90 RBT1 0.01 0.010.01 0.01 RBT2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 pTPP 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 TPP 0.50 0.50 0.50 0.50

TABLE 2 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Si1 26 32 26 26 29 2929 29 29 30 30 31 26 21 Si2 10 10 10 8 8 8 8 8 7 7 5 10 15 Si3 2 4 VMA40 45 40 40 42 44 45 42 45 44 45 40 40 40 DMA HEMA 4 HOB 7 BVE 7 3 7 3 45 9 9 9 DEGVE 7 7 10 EGVE 5 MMA 13 12 12 14 14 13 8 8 12 10 10 10 EGMA15 3 5 5 6 10 6 5 5 5 5 TEGDVE 0.20 0.20 0.20 0.10 0.08 0.15 0.10 0.100.10 0.10 0.20 0.10 0.10 0.10 EGDMA 0.50 0.60 0.60 0.50 0.60 0.50 0.601.00 TEGDMA 1.60 1.00 1.20 1.40 1.00 1.00 AE 0.3 0.4 0.3 V64 0.50 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 UV2 0.901.30 1.30 1.30 1.30 1.30 1.70 1.70 1.70 1.80 1.80 0.90 0.90 0.90 UV1RBT1 0.01 0.01 RBT2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.010.01 0.01 pTPP 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.500.50 0.50 TPP

TABLE 3 Lens Processing and Formulation Number Properties 1 2 3 4 5 6 78 9 10 11 12 13 14 Demolding Process Dry Dry Dry Dry Dry Dry Dry Dry DryDry Dry Dry Dry Dry Used Delensing Process Dry Dry Dry Dry Dry Dry DryDry Dry Dry Dry Dry Dry Dry Used Extraction Media O* O* O* O* O* A* A*A* A* A* A* A* A* A* Used EWC (%) 52 52 53-54 53 55 58 55 58 56 57 55 54Dynamic CA (°) 50.10 50.00 48-52 Static CA (°) 30 38 37 WBUT(sec.) >20 >20 >20 >20 >20 >20 >20 Modulus (MPa) 0.63 0.58 0.43 0.400.70 0.77 0.61 0.66 0.57 0.69 0.85 0.66 0.81 Ionoflux (×10⁻³ 3.622.5-3.0 2.90 3.10 4.14 4.19 2.75 3.54 3.68 3.06 3.57 mm₂/min) Dk(barrers) 70 >60 72 Elongation (%) 450 425 345 349 275 216 310 314 284274 351 Tensile Strength 1.40 1.40 2.40 1.75 1.51 0.87 1.90 1.30 1.881.40 1.61 (MPa) Transmittance (%) 98.00 98.00 Wet Ext. (%) 0.67 1.231.30 3.90 4.42 4.10 4.56 4.47 1.81 2.38 3.80 Dry Ext. (%) 17.00 11.0014.39 Energy Loss (%) 36 35-36 40 41 34-36 34 36 Swell Factor (%) 21 21A* = extracted in a volatile organic solvent-free extraction media O* =extracted in volatile organic solvent-based media and volatile organicsolvent-free media

TABLE 4 Lens Processing and Formulation Number Properties 15 16 17 18 1920 21 22 23 24 25 26 27 28 Demolding Process Dry Dry Dry Dry Dry Dry DryDry Dry Dry Dry Dry Dry Dry Used Delensing Process Dry Dry Dry Dry DryDry Dry Dry Dry Dry Dry Dry Dry Dry Used Extraction Media A* A* A* A* A*A* A* A* A* A* A* A* A* A* EWC (%) 53 57 56 55 55-56 56 55-56 57-5855-56 61 55-57 56 Dynamic CA (°) 50-56 47-51 47-55 45-47 51-53 44-4855-58 45-47 47-53 Static CA (°) WBUT (sec.) Modulus (MPa) 0.74 0.70 0.500.60 0.71 0.65 0.53 0.70 0.60 0.50 0.70 0.46 0.51 Ionoflux (×10⁻³ 3.332.90 4.10 3.80 3.60 3.60 6.42 mm₂/min) Dk (barrers) 59-71 59-67 81Elongation (%) 222 300 275 279 285 196 200 Tensile Strength 1.50 1.201.20 1.30 0.60 0.67 (MPa) Transmittance (%) A* Wet Ext. (%) 5.10 4.604.55 4.10 7.28 Dry Ext. (%) 12.20 10.60 13.65 9.80 17.87 Energy Loss (%)40 34 32-33 31-32 30-33

4.1-35.

36-38 34-38 32-34 Swell Factor (%) 27 A* = extracted in a volatileorganic solvent-free extraction media O* = extracted in volatile organicsolvent-based media and volatile organic solvent-free media

indicates data missing or illegible when filed

Examples 29-37

Table 5 lists the ingredients of polymerizable compositions 29-37.Polymerizable compositions 29-37 were prepared as described in theHydrogel Contact Lens Fabrication and Testing Procedure given above, andwere used to prepare and test hydrogel contact lenses as described inthe Hydrogel Contact Lens Fabrication and Testing Procedure. All ofthese lenses were demolded using a dry demolding process, delensed usinga dry delensing process, and extracted using liquid free of a volatileorganic solvent. With the exception of polymerizable compositions 29, 32and 35, all of the polymerizable compositions include aphosphine-containing component (either TPP or pTPP).

Table 6 shows the lens properties for lenses formed using polymerizablecompositions 29-37 when initially manufactured. Hydrogel contact lensesformed from polymerizable compositions 30, 31, 33, 34, 36 and 37 (thelenses formed from a polymerizable composition with aphosphine-containing component) had acceptable lens properties wheninitially manufactured. As can be seen from Table 6, the lens propertiesof the lenses formed from formulations containing thephosphine-containing component were similar to the lens properties ofthe lenses formed from the same formulations except without thephosphine-containing components when prepared using the samemanufacturing process. The lenses of formulations 30, 31, 33, 34, 36 and37 also had acceptable shape retention and color value both wheninitially manufactured and for at least 1 month when stored at roomtemperature. The lenses formed from formulations without thephosphine-containing component, however, did not have acceptable shaperetention or AEL when initially manufactured.

Formulations 30 and 31 were also used to prepare lenses using apreparation process as described in the Hydrogel Contact LensFabrication and Testing Procedure, demolded using a dry demoldingprocess, delensed using a dry delensing process, and extracted usingliquid free of a volatile organic solvent, except that the lenses werecured under an air atmosphere. The air-cured lenses had similar lensproperties as air-cured lenses prepared from the same formulation exceptwithout the phosphine-containing component (formulation 29). However,the lenses of formulations 30 and 31 had acceptable shape retention(including acceptable AEL) and color value when air-cured, while thelenses of formulation 29 did not have acceptable shape retention oracceptable AEL when air-cured.

TABLE 5 Ingredient Formulation Number (unit parts) 29 30 31 32 33 34 3536 37 Si4 35 35 35 25 25 25 20 20 20 Si5 25 25 25 Si6 25 25 25 25 25 25VMA 40 40 40 30 30 30 DMA 40 40 40 10 10 10 20 20 20 TEGDVE 0.1 0.1 0.1TEGDMA 0.8 0.8 0.8 0.6 0.6 0.6 AE V64 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.30.3 Glycerol 3 3 3 pTPP 0.5 0.5 0.5 TPP 0.5 0.5 0.5

TABLE 6 Formulation Number Lens Properties 29 30 31 32 33 34 35 36 37 N₂Cured Lenses Modulus (MPa) 0.27 0.25 0.23 0.32 0.36 0.36 0.42 0.41 0.40Tensile Strength (MPa) 0.67 0.78 0.74 0.51 0.70 0.63 Elongation (%) 379466 476 192 217 208 Air Cured Lenses Modulus (MPa) 0.21 0.25 0.23Tensile Strength (MPa) 0.44 0.85 1.1 Elongation (%) 327 489 519

Although the disclosure herein refers to certain illustratedembodiments, it is to be understood that these embodiments are presentedby way of example and not by way of limitation. The intent of theforegoing detailed description, although discussing exemplaryembodiments, is to be construed to cover all modifications,alternatives, and equivalents of the embodiments as may fall within thespirit and scope of the invention as defined by the additionaldisclosure.

A number of publications and patents have been cited hereinabove. Eachof the cited publications and patents are hereby incorporated byreference in their entireties.

1. A method of manufacturing a hydrogel contact lens, comprising:providing a polymerizable composition comprising (a) at least onehydrophilic monomer, and (b) at least one phosphine-containing compound,wherein the at least one phosphine-containing compound is present in anunoxidized form at the time it is combined with the at least onehydrophilic monomer in the polymerizable composition; and reacting thepolymerizable composition to form a polymeric lens body.
 2. The methodof claim 1, wherein the phosphine-containing compound has a structurerepresented by formula (1):

where X1, X2, and X3 are the same or different and are an alkyl group oran aryl group.
 3. The method of claim 1, wherein thephosphine-containing compound is a polymerizable phosphine-containingcompound.
 4. The method of any claim 1, wherein the phosphine-containingcompound comprises triphenylphosphine, ordiphenyl(4-vinylphenyl)phosphine, or both.
 5. The method of claim 1,wherein the phosphine compound is present in the polymerizablecomposition in an amount from 0.01 to 5 unit parts.
 6. The method ofclaim 1, wherein the polymerizable composition contains an amount of thephosphine-containing compound effective to scavenge at least a portionof oxygen present in the polymerizable composition during themanufacturing.
 7. The method of claim 1, wherein the polymerizablecomposition contains an amount of the phosphine-containing compoundeffective to produce a polymeric lens body having a reduced amount ofaxial edge lift (AEL) as compared to a second hydrogel contact lens bodyformed from a second polymerizable composition substantially identicalto the polymerizable composition except without the phosphine-containingcompound and using a manufacturing process substantially identical tothe manufacturing process of the hydrogel contact lens.
 8. The method ofclaim 1, wherein the polymerizable composition contains an amount of thephosphine-containing compound effective to reduce distortion of thehydrogel contact lens as compared to a second hydrogel contact lens bodyformed from a second polymerizable composition substantially identicalto the polymerizable composition except without the phosphine-containingcompound and using a manufacturing process substantially identical tothe manufacturing process of the hydrogel contact lens.
 9. The method ofclaim 1, wherein the reacting of the polymerizable composition isconducted in an atmosphere comprising air.
 10. The method of claim 1,wherein the reacting of the polymerizable composition is conducted in anatmosphere comprising an inert gas at a concentration greater than isfound in air.
 11. The method of claim 1, wherein the polymerizablecomposition contains an amount of the phosphine-containing compoundeffective to reduce discoloration of the contact lens for at least 1year when stored at room temperature, as compared to a second contactlens formed from a second polymerizable composition substantiallyidentical to the first polymerizable composition except without thephosphine-containing compound and using a manufacturing processsubstantially identical to the manufacturing process of the hydrogelcontact lens.
 12. The method of claim 1, wherein the polymerizablecomposition further comprises at least one siloxane monomer.
 13. Themethod of claim 1, wherein the reacting comprises cast molding thepolymerizable composition in a contact lens mold assembly to form apolymeric lens body.
 14. The method of claim 1, further comprisingcontacting the polymeric lens body with a washing liquid to removeextractable material from the polymeric lens body.
 15. The method ofclaim 14, wherein the contacting removes a portion of the at least onephosphine compound from the polymeric lens body.
 16. The method of claim1, further comprising oxidizing at least a portion of thephosphine-containing compound present in the polymeric lens body, or inthe hydrogel contact lens.
 17. A hydrogel contact lens, comprising: apolymeric lens body that is the reaction product of a polymerizablecomposition, the polymerizable composition comprising (a) at least onehydrophilic monomer, and (b) at least one phosphine-containing compound,wherein the at least one phosphine-containing compound is present in anunoxidized form at the time it is combined with the at least onehydrophilic monomer in the polymerizable composition.
 18. A batch ofhydrogel contact lenses comprising a plurality of hydrogel contactlenses made in accordance with the method of claim
 17. 19. The batch ofhydrogel contact lenses of claim 18, wherein the batch of hydrogelcontact lenses has an average axial edge lift (AEL) variance of lessthan plus or minus 50% over a time period from two weeks to seven yearswhen stored at room temperature, or, when stored under accelerated shelflife conditions for a time period and temperature equivalent to storagefrom two weeks to seven years at room temperature, as determined basedon at least 20 individual lenses of the batch, the AEP variancepercentage determined for each of the individual lenses by the followingequation (A):((AEL_(Final)−AEL_(Initial))/AEL_(Initial))×100  (A).
 20. A hydrogelcontact lens package, comprising: a polymeric lens body that is thereaction product of a polymerizable composition, the polymerizablecomposition comprising (a) at least one hydrophilic monomer, and (b) atleast one phosphine containing compound wherein the at least onephosphine-containing compound is present in an unoxidized form at thetime it is combined with the at least one hydrophilic monomer in thepolymerizable composition; a packaging solution comprising a lenshydrating agent; and a contact lens package base member having a cavityconfigured to hold the contact lens body and the packaging solution, anda seal attached to the base member configured to maintain the contactlens and the packaging solution in a sterile condition for a duration oftime equivalent to a room temperature shelf life of the contact lens.